CN110280313A - A kind of three-dimensional structure load TiO2-xThe preparation method of material - Google Patents
A kind of three-dimensional structure load TiO2-xThe preparation method of material Download PDFInfo
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- CN110280313A CN110280313A CN201910624758.5A CN201910624758A CN110280313A CN 110280313 A CN110280313 A CN 110280313A CN 201910624758 A CN201910624758 A CN 201910624758A CN 110280313 A CN110280313 A CN 110280313A
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910003081 TiO2−x Inorganic materials 0.000 claims abstract description 95
- 239000004417 polycarbonate Substances 0.000 claims abstract description 76
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910001868 water Inorganic materials 0.000 claims abstract description 53
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 239000007921 spray Substances 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000006229 carbon black Substances 0.000 claims description 120
- 238000007639 printing Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 16
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
- 239000002127 nanobelt Substances 0.000 claims description 8
- 238000010146 3D printing Methods 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 abstract description 25
- 230000008020 evaporation Effects 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 22
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 description 26
- 230000015556 catabolic process Effects 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 25
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- 230000008859 change Effects 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
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- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 239000002384 drinking water standard Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
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- 230000031700 light absorption Effects 0.000 description 2
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- 239000013535 sea water Substances 0.000 description 2
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- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 1
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- 239000003651 drinking water Substances 0.000 description 1
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- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/205—Means for applying layers
- B29C64/209—Heads; Nozzles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/245—Platforms or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/295—Heating elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/321—Feeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/386—Data acquisition or data processing for additive manufacturing
- B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Abstract
A kind of three-dimensional structure load TiO2‑xThe preparation method of material belongs to photocatalysis technology field.The invention solves TiO2The technical issues of photocatalysis efficiency is low and powder difficult recycling.The method of the present invention: one, CB/TiO is prepared2‑xPowder；It two, is that raw material prepares PC cone with polycarbonate (PC)；Three, by step 1 CB/TiO2‑xPowder is dissolved in organic solvent, and ultrasonic treatment obtains CB/TiO2‑xSuspension pours into suspension in spray gun, and at least 3 layers of even application in PC cone, are then rinsed with deionized water, vacuum drying.The present invention improves TiO2Photocatalysis performance while assign its Driven by Solar Energy water evaporation performance and can not only maximally utilise solar energy for producing clean water, can also realize the water process of Double function high efficient.
Description
Technical field
The invention belongs to photocatalysis technology fields；More particularly to polycarbonate load C B/TiO2-xThe preparation method of material.
Background technique
Global water resources scarcity and pollution problem have seriously affected the development of human society.Skill currently used for sewage purification
Art is varied, and the process for purifying water of single principle is often unable to reach efficient clean-up effect, and can also consume a large amount of
Financial resource and material resource.It can be carried out wastewater treatment, including photocatalysis degradation organic contaminant and Driven by Solar Energy water evaporation using the sun, be
Solve the problems, such as this effective way.
Photocatalytic degradation and Driven by Solar Energy water evaporation are considered as solving clean water resources shortage problem most to have prospect
Technology.Although having put into many effort to explore efficiently production clean water, there are with high costs, dirt-removing functions for the prior art
The single and inferior problems of low efficiency, and then significantly limited to it and promoted and apply.It is therefore difunctional that (photocatalysis and water steam
Hair) it is integrated into same composite material for producing clean water, solar energy can be not only utilized to greatest extent, acceptable reality
The water process of existing Double function high efficient.
TiO2It is led because its is environment-protecting and non-poisonous, stability is good and has high activity site in photocatalysis as a kind of photochemical catalyst
Domain causes the extensive concern of people.But due to TiO2Forbidden bandwidth is larger, leads to that its optical response range is narrow, quantum efficiency is low, sternly
Ghost image rings photocatalytic activity, and TiO2The recycling problem of powder catalyst, significantly impacts its catalytic effect and practicability.Though
So by can be to avoid its recycling by photochemical catalyst solidification the problem of, but realize that effectively immobilized there is still a need for exploration, photocatalytics
It can need to be improved.
Summary of the invention
The invention solves TiO2The technical issues of photocatalysis efficiency is low and powder difficult recycling；Provide a kind of three-dimensional knot
Structure loads TiO2-xThe preparation method of material.
The present invention improves TiO2Photocatalysis performance while assign its Driven by Solar Energy water evaporation performance, it is clear for producing
Clean water can not only maximally utilise solar energy, can also realize the water process of Double function high efficient.
In order to solve the above technical problems, a kind of three-dimensional structure load TiO in the present invention2-xThe preparation method of material is to press
State step progress:
Step 1: carbon black (CB) is added in Tris buffer (pH=8.5,50mM), it is ultrasonically treated 30min, and to it
It is stirred, TiO is then added2-x, continue to stir, after liquid to be mixed is uniform, it is mixed that the Dopamine hydrochloride that concentration is 2mg/mL be added
Conjunction stirs evenly, and is subsequently placed in shaking table, is passed through air in concussion, handles 12h, be washed with deionized for several times, and 60 DEG C true
Sky drying, obtains CB/TiO2-xPowder；
Step 2: 3D printing hollow cone successively carries out destressing, oil removal treatment with polycarbonate (PC) for raw material,
Then it is rinsed well with deionized water, then impregnates in dehydrated alcohol and handle 10min, it is 50mM that concentration is directly transferred to after taking-up
Tris-HCl buffer in, then be added Dopamine hydrochloride (2mg/mL), vacuum drying, obtain PC cone；
Step 3: by step 1 CB/TiO2-xPowder is dissolved in organic solvent, ultrasonic treatment, and 10~20mg/mL of configuration is dense
The CB/TiO of degree2-xSuspension pours into suspension in spray gun, and at least 3 layers of even application in PC cone, are then used deionization
Water rinses, and is dried in vacuo 4h at 30 DEG C to get to three-dimensional structure and loads TiO2-xThe preparation method of material.
It further limits, TiO described in step 12-xIt is prepared according to the following steps:
Step 1: taking 0.6gP25 to be dissolved in the NaOH solution that 60mL concentration is 10mol/L, be transferred to water after ultrasonic 30min
In hot kettle, then 12~48h of hydro-thermal process at 200 DEG C uses deionization to pH value to 2.0 ± 0.2 with the salt acid elution of 0.1M
It is washed repeatedly after water washing is multiple with dehydrated alcohol, dry 12h, is then placed in tube furnace, at 500 DEG C under 60 DEG C of vacuum conditions
Lower calcining 4h, natually cooled to room temperature obtain white TiO2Nanobelt；
Step 2: taking white TiO made from 0.2g step 12Nanobelt is added 0.4g sodium borohydride, is fully ground mixing
After uniformly, it is put into tube furnace, in argon atmosphere, with 5 DEG C of min-1Heating rate be warming up to 300~450 DEG C, heat preservation
Mixture is dissolved in deionized water by 3h, cooled to room temperature, filters, washing, 70 DEG C of vacuum drying 12h, black is made
TiO2-xNanobelt.
It further limits, with 5 DEG C of min in step 2-1Heating rate be warming up to 360 DEG C.
It further limits, CB and TiO in step 12-xMass ratio be 1:(1~5), CB mass and Tris buffer volume
Ratio be (0.05~0.5) g:(10~100) mL, the ratio of CB mass and Dopamine hydrochloride volume is (2~10) g:1mL.
It further limits, specific step is as follows for 3D printing hollow cone in step 2:
PC silk material is put into 60 DEG C of vacuum drying treatment 12h before printing, is set using 3D Max (3D Studio Max) software
Target print underlying structure is counted out, carries out printing after 3D printer identifies this file, the nozzle diameter of printer is
0.4mm, nozzle temperature are set as 260 DEG C, and printing machine platform is set as 90 DEG C, and room temperature is 80 DEG C, does not use any adhesive, leads to
It crosses two pinch rollers and 1.75mm monofilament is sent into FDM printer, layer print speed is maintained at 1.5m/min, and layer height is set as
0.05mm, then successively printing, obtains hollow cone.
It further limits, the apex angle of hollow cone described in step 2 is 60 °~120 °.
It further limits, is dried in vacuo 12h at 45 DEG C in step 2.
It further limits, organic solvent is dehydrated alcohol in step 3.
It further limits, the coating layer thickness after spraying in step 3 in PC cone is 6 μm.
It further limits, step 3 is dried in vacuo 4h at 30 DEG C.
Three-dimensional structure of the present invention loads TiO2-xMaterial can realize the efficient degradation (99.94%) to MG solution in 2min,
Significant change does not occur for its catalytic activity after 20 circulations, sufficiently stable as catalysis material.
Three-dimensional structure of the present invention loads TiO2-xMaterial is due to TiO2-xNanometer band structure, the presence of CB and Ti3+With oxygen sky
The synergistic effect of the introducing of position, makes it have more excellent photocatalysis performance.
Three-dimensional structure of the present invention loads TiO2-xMaterial has good Driven by Solar Energy water evaporation ability, due to superpower light
Absorbent properties (99.68%), being lauched evaporation rate in 3 times of sunlights is 4.5371kg/ (m2H), photothermal conversion efficiency reaches
93.52%.Use CB/TiO2-x/ PC carries out sea water desalination experiment, the evaporation water intermediate ion (Na of collection+、Mg2+、K+、Ca2+) concentration
Show that 4 orders of magnitude successively decrease (2.1mg/L), better than the drinking water standard of WHO defined.
Detailed description of the invention
Fig. 1 is that embodiment 1 prepares TiO2-xTEM photo；A) 2 μm of TEM shine, b) 200nmTEM photo；c)50nmHRTEM
Photo, d) 5nmHRTEM photo；
Fig. 2 is sample TiO2(P25)、TiO2、TiO2-xUV-Vis-NIR absorb map；
Fig. 3 is the CB/TiO of different synthesis mass ratioes2-xSEM photograph, a) CB and TiO2-xMass ratio be 1:1, b) CB
With TiO2-xMass ratio be 1:2, c) CB and TiO2-xMass ratio be 1:3, d) CB and TiO2-xMass ratio be 1:4, e) CB with
TiO2-xMass ratio be 1:5；
Fig. 4 is CB/TiO2-xSEM photograph and corresponding mapping a) CB/TiO2-xFigure；b)Ti；c)O；d)C；
Fig. 5 is the CB/TiO of different synthesis mass ratioes2-xUV-Vis-NIR absorb map；
Fig. 6 is CB/TiO2-xPhotocatalytic mechanism schematic diagram；
Fig. 7 is the pictorial diagram of the PC cone of different apex angles, a) 60 ° of apex angle, b) 90 ° of apex angle, c) 120 ° of apex angle；
Fig. 8 be under different printing technology PC 3D bore pictorial diagram and SEM photograph a), b), c) be technique 1,3 and 5 material object
Figure；D), e), f) scheme for the SEM of technique 1,3 and 5；
CB/TiO after the spraying of Fig. 9 embodiment 12-xThe UV-Vis-NIR of/PC absorbs spectrogram；
Figure 10 is the photocatalytic activity of different samples under illumination；
Figure 11 is different CB/TiO2-xSpray the corresponding CB/TiO of the number of plies2-x/ PC catalytic performance；
Figure 12 is the water evaporation mass loss change curve of different samples；
Figure 13 is Na before and after desalination+, Ca2+, K+And Mg2+Salinity；
Figure 14 is CB/TiO2-xThe catalytic degradation stability of/PC；
Figure 15 is CB/TiO2-xThe water evaporation stability of/PC；
Figure 16 is CB/TiO2-xThe efficient Water clarifying mechanism schematic diagram of/PC.
Specific embodiment
Embodiment 1: raw material TiO in the present embodiment2-xIt is prepared according to the following steps:
Step 1: taking 0.6gP25 to be dissolved in the NaOH solution that 60mL concentration is 10mol/L, be transferred to water after ultrasonic 30min
In hot kettle, then the hydro-thermal process 36h at 200 DEG C is washed with deionized water with the salt acid elution of 0.1M to pH value to 2.0 ± 0.2
It is washed repeatedly after washing repeatedly with dehydrated alcohol, dry 12h, is then placed in tube furnace, forges at 500 DEG C under 60 DEG C of vacuum conditions
4h is burnt, natually cooled to room temperature obtains white TiO2Nanobelt, growth is more uniform, and pattern is that size is about 4 μm of band-like knots
Structure；
Step 2: taking white TiO made from 0.2g step 12Nanobelt is added 0.4g sodium borohydride, is fully ground mixing
After uniformly, it is put into tube furnace, in argon atmosphere, with 5 DEG C of min-1Heating rate be warming up to 350 DEG C, keep the temperature 3h, it is natural
It is cooled to room temperature, mixture is dissolved in deionized water, filter, washing, 70 DEG C of vacuum drying 12h, black TiO is made2-xNanometer
Band, band-like pattern, and contain Ti3+And Lacking oxygen, malachite green solution can be degraded (99.94%) in 40min, degradation rate
Meet first _ order kinetics equation, rate constants k 0.05692min-1, about TiO2(NBs) 5 times.
A kind of three-dimensional structure load TiO in the present embodiment2-xThe preparation method of material carries out in the steps below:
Step 1: carbon black (CB) is added in Tris buffer (pH=8.5,50mM), it is ultrasonically treated 30min, and to it
It is stirred, TiO made from the above method is then added2-x, continue to stir, after liquid to be mixed is uniform, addition concentration is 2mg/mL
Dopamine hydrochloride be mixed evenly, be subsequently placed in shaking table, be passed through air in concussion, handle 12h, be washed with deionized water
It washs for several times, 60 DEG C of vacuum dryings obtain CB/TiO2-xPowder；
The ratio of CB mass and Tris buffer volume is 0.1g:50mL, CB mass and Dopamine hydrochloride volume in step 1
Ratio be 5g:1mL.
It can be achieved in 3min to MG solution degradation 99.95%.Through five times circulation after, catalytic activity remain at 89% with
On, catalyst performance is more stable
Step 2: 3D printing hollow cone successively carries out destressing, oil removal treatment with polycarbonate (PC) for raw material,
Then it is rinsed well with deionized water, then impregnates in dehydrated alcohol and handle 10min, it is 50mM that concentration is directly transferred to after taking-up
Tris-HCl buffer in, then be added Dopamine hydrochloride (2mg/mL), be dried in vacuo 12h at 45 DEG C, obtain PC cone；
Step 3: by step 1 CB/TiO2-xPowder is dissolved in dehydrated alcohol, ultrasonic treatment, configuration 15mg/mL concentration
CB/TiO2-xSuspension pours into suspension in spray gun, and 3 layers of even application in PC cone, are then rinsed with deionized water,
It is dried in vacuo 4h at 30 DEG C and loads TiO to get to three-dimensional structure2-xThe preparation method of material (is labeled as CB/TiO2-x/PC)；
Wherein specific step is as follows for 3D printing hollow cone in step 2:
PC silk material is put into 60 DEG C of vacuum drying treatment 12h before printing, is set using 3D Max (3D Studio Max) software
Target print underlying structure is counted out, carries out printing after 3D printer identifies this file, the nozzle diameter of printer is
0.4mm, nozzle temperature are set as 260 DEG C, and printing machine platform is set as 90 DEG C, and room temperature is 80 DEG C, does not use any adhesive, leads to
It crosses two pinch rollers and 1.75mm monofilament is sent into FDM printer, layer print speed is maintained at 1.5m/min, and layer height is set as
0.05mm, then successively printing, obtains the hollow cone that apex angle is 60 °.
The resulting CB/TiO of the present embodiment2-x/ PC can realize the efficient degradation (99.94%) to MG solution in 2min, warp
Significant change does not occur for its catalytic activity after crossing 20 circulations, sufficiently stable as catalysis material.
The resulting CB/TiO of the present embodiment2-x/ PC has good Driven by Solar Energy water evaporation ability, since superpower light is inhaled
It receives performance (99.68%), being lauched evaporation rate in 3 times of sunlights is 4.5371kg/ (m2H), photothermal conversion efficiency reaches
93.52%.Use CB/TiO2-x/ PC carries out sea water desalination experiment, the evaporation water intermediate ion (Na of collection+、Mg2+、K+、Ca2+) concentration
Show that 4 orders of magnitude successively decrease (2.1mg/L), better than the drinking water standard of WHO defined.
The present embodiment method obtains TiO2-xTEM photo it is as shown in Figure 1.It can be seen that sample presentation is band-like knot
Structure, in TiO2-xHRTEM image, discovery can observe TiO in magnification at high multiple image2Lattice fringe and amorphous outer
Shell, the corresponding 0.35nm lattice fringe of discovery is TiO2(100) crystal face.TiO2-xAmorphous shell peomote electricity
Son transfer and separation, to promote the photocatalysis performance of catalyst.
The present embodiment method obtains TiO2-xUV-Vis-NIR absorb map it is as shown in Figure 2.TiO2-xIn 400nm-
2500nm is compared to TiO2And TiO2There is stronger absorption, entire sunlight wave spectral limit is widened to the response of light, illustrates certainly
TiO after doping vario-property2-xAbsorbing properties have occurred biggish change, and this strong absorption is attributable to that there are Ti3+Mix certainly
It is miscellaneous, make TiO2-xForbidden bandwidth decrease.
The CB/TiO of difference synthesis mass ratio2-xSEM photograph as shown in figure 3, on the whole PDA effect under CB it is real
Show and TiO2-xIt is compound, but due to the difference for being initially added CB ratio cause load the case where different from.Such as Fig. 3 a institute
Show, fairly large agglomeration occurs for CB, and the amount for being mainly due to the CB being initially added is more, additionally, due to the effect of PDA
CB is set largely to be reunited.With the reduction that CB amount is added, agglomeration obtains different degrees of decrease, and Fig. 3 b is
SEM image when 1:2 can be seen that CB is successfully carried on TiO2-x, and comparatively load it is more uniform, to its photocatalysis drop
It is advantageous to solve performance, this point available confirmation in next performance test.Scheming c is CB and TiO2-xLoad percentage is
SEM image when 1:3 observes that the amount of CB significantly reduces, and agglomeration is significantly improved.Fig. 3 d, e are respectively corresponded
Be load quality ratio be 1:4 and 1:5 when SEM image, the amount of CB largely reduced at this time, but still be observed that CB at
Function is carried on TiO2-xOn, it is comparatively still more uniform.According to the pattern of Fig. 3 a, b, c, d, e change as can be seen that with
The difference of initial CB amount, load effect is different, but from the appearance from the point of view of in black, absorbing properties can not
Together.
CB/TiO is obtained in the present embodiment step 12-xSEM photograph and corresponding mapping it is as shown in Figure 4.It can be bright
Aobvious finds out CB/TiO2-xIt is made of tri- kinds of elements of Ti, O, C, it can also be seen that the SEM that the distribution of Ti and O element is corresponding
TiO in figure2-xConsistent appearance, and C element is evenly distributed on TiO2-xThe region at place, this test result show CB success
With TiO2-xIt is loaded, CB/TiO has successfully been made2-x。
CB/TiO is obtained in the present embodiment step 32-xUV-Vis-NIR absorb map it is as shown in Figure 5.It can be observed that
CB in the absorption of 400nm-2500nm be it is stronger, as CB and TiO2-xAfter success is compound, they are interacted with each other, the two
Photo absorption performance be all improved, successfully load after CB/TiO2-xPhoto absorption performance is compared to the two extinction before unsupported
Performance increases, and the absorbing properties of full spectral coverage are all very balanced at 250nm-2500nm.And it was found that with CB
Its photo absorption performance of the increase of content is gradually increasing, but be not CB its higher photo absorption performance of content it is stronger.
CB/TiO is obtained in the present embodiment step 32-xPhotocatalytic mechanism as shown in fig. 6, with Ti3+With drawing for Lacking oxygen
Enter, in CB/TiO2-xConduction band below form new impurity energy level, this will make CB/TiO2-xBand gap narrow, thus enhancing to too
The photoresponse of sunlight.On the other hand, carbon black (CB) is also to improve an important factor for photocatalysis efficiency should not be ignored, because it is increasing
It is played a crucial role in the separation of strong adsorption capacity, electronics transfer and photo-generate electron-hole pair.When catalyst is exposed to
When under illumination, in TiO2-xValence band (VB) in will generate a large amount of light induced electron, and be immediately transferred to TiO2-xIn Ti3+Defect
In Lacking oxygen, hole is left in VB.TiO2-xIn be excited to Ti3+E in defect and Lacking oxygen-, can be by fast transfer
Onto CB, and finally with the OH in solution-And H2O reaction generates OH free radical.Meanwhile OH-And H2O is by TiO2-xVB in
Hole capture generates OH free radical.Finally, organic pollutant can be with free radical such as OH, O2 -Reaction generate to environment without
Harmful small-molecule substance.The Rapid Circulation system of this photo-generate electron-hole pair accelerates the transfer of electronics, reduce electronics and
The recombination rate in hole.In catalytic reaction process, Lacking oxygen can provide absorption of the dangling bonds for reaction substrate；Due to tool
Have a characteristic of local electron rich, Lacking oxygen can also the inert chemi-cal key to immunoabsorbent substrate activate, regulate and control its electronic structure,
To greatly influence photocatalytic process.In addition, TiO2-xNanobelt pattern also contributes to improving photocatalytic activity, because it has
There is biggish specific surface area, Adsorption can be increased, be conducive to the absorption of pollutant, and improves daylighting effect to the maximum extent
Rate.Therefore, TiO2-xNanometer band structure, the presence of CB, Ti3+CB/ is helped to improve with the synergistic effect of the introducing of Lacking oxygen
TiO2-xPhotocatalysis performance.
The pictorial diagram of the PC cone of different apex angles is as shown in Figure 7.
The printing technology parameter of PC 3D cone in the present embodiment step 4 is as shown in table 1.PC 3D under different printing technology
The pictorial diagram and SEM photograph of cone are as shown in Figure 8.A, b, c be respectively in technique 1 in Fig. 8, technique 3 and technique 5 these three process conditions
Made from descending, it can be seen that figure c is more smooth in appearance by comparing, it is more closely knit, and surface does not occur due to cooling down not in time
Caused by rugged phenomenon, accurately find out its microstructure to more be illustrated, can by their corresponding SEM pictures
To find that the microstructure of the microcosmic sample printed under the conditions of the present embodiment more has lines and orderliness is more clear,
The material surface printed it is relatively smooth, stereovision is stronger, the characteristics of meeting FDM printing technique.
The printing technology parameter of 1 PC 3D of table cone
CB/TiO after obtaining best spraying process in the present embodiment step 32-xThe UV-Vis-NIR of/PC absorbs map such as
Shown in Fig. 9.By the screening of a series of spray parameters, the application has determined optimal spray parameters, uses concentration for 15mg/
The CB/TiO of mL2-xAlcohol dispersion liquid PC three-dimensional structure is sprayed, spray 3 layers of the number of plies.Absorbing properties after spraying are such as
Shown in Fig. 9, it is shown that the variation of the absorbing properties of spraying front and back PC cone, the PC three-dimensional structure before not spraying is in 250nm-
The average light absorption rate of 2500nm has reached about 97%, and has loaded CB/TiO2-xPC three-dimensional structure CB/TiO2-x/ PC is multiple
It closes catalyst and has reached 99.67% in the full wave absorptivity of sun wave spectrum, there is more excellent photo absorption performance.
CB/TiO obtained in the present embodiment step 52-xThe analysis of/PC photocatalysis performance as shown in Figure 10, can from Figure 10 (a)
To find out that the PC of blank because having certain pollution adsorption capacity after the processing of the hydrophily of PDA, but CB is carried out with it
After load, catalytic performance does not occur significantly to improve, this is primarily due to CB without photocatalytic degradation capability, but will
CB/TiO2、CB/TiO2/ PC three-dimensional structure load after, it is found that its catalytic degradation ability is promoted, this is mainly due to PC
Its absorbing properties has and is enhanced after three-dimensional structure is negative.In contrast to this by CB/TiO2-xAfter/PC three-dimensional structure carries again, hair
Existing CB/TiO2-xThe catalytic degradation ability of/PC is compared to CB/TiO2-xThere is improvement, it can be in 2min degradation 99.94%MG, mainly
Because the degradation of MG pollutant is related with temperature, and by testing the CB/TiO in catalytic process2-xThe temperature of/PC is up to 72 DEG C
Left and right.Therefore it to the catalytic degradation of MG and not up to preferably makes moderate progress.If Figure 10 (b) is that different catalyst samples exist
To the degradation percentage of MG in 2min, from the palliating degradation degree that can clearly compare each catalyst in 2min in figure, at this time only
There is CB/TiO2-x/ PC realizes 99.94%.Figure 10 (c) is degradation kinetics curve of each catalyst to MG organic pollutant, by
Figure can illustrate that this degradation process meets first _ order kinetics equation, and CB/TiO2-xThe observed rate constant k of/PC is much larger than
TiO2/PC。
Different CB/TiO2-xSpray the corresponding CB/TiO of the number of plies2-x/ PC catalytic performance is as shown in figure 11, different from Figure 11
The corresponding degradation curve variation of sample is it can be seen that CB/TiO2-x/ PC is to MG solution catalyzing degradation capability, as spraying CB/TiO2-x
When the number of plies changes in a certain range, CB/TiO2-x/ PC to the degradation property of MG solution can with spraying the number of plies increase and by
It is cumulative strong, but after spraying the number of plies more than this range, CB/TiO2-x/ PC will no longer change the degradation property of MG solution
Become.This is primarily due to when the amount of catalyst increases in a certain range, can provide more active sites for reaction；Together
When, the unit time interior more electron-hole pairs of generation；Therefore, there can be greater number of organic molecule in the same time
Reaction is participated in, this can undoubtedly improve the efficiency of photocatalytic degradation reaction.But after catalyst amount increases to a certain extent, at this time
Increase the amount of catalyst again, photocatalytic activity will no longer change, this is primarily due to, after catalyst is sprayed in substrate
The case where there are adsorption saturations is further added by the amount of catalyst after reaching adsorption saturation, to catalysis reaction carry out rate without bright
Aobvious facilitation.Work as CB/TiO2-xThe spraying number of plies from 1 layer change to 5 layers during, discovery when catalyst spraying the number of plies be 3
When layer, under the irradiation of Xe lamp source, the MG solution degradation 99.94% that can be 10mg/mL by concentration in 2min.When the spraying number of plies
When greater than 3 layers, CB/TiO2-x/ PC does not substantially change the degradation property of MG solution；When the spraying number of plies becomes at 1 to 3 layers
Change, can obviously observe its change to MG degradation property；When the spraying number of plies is 1,2 layer, it can degrade respectively in 15min, 10min
99.92%, 99.93% MG.
CB/TiO obtained in the present embodiment step 52-x/ PC water evaporation performance evaluation is as shown in figure 12, with Xe lamp source
The unit area evaporated quantity of water versus time curve of different samples under simulated solar irradiation irradiation.The application tests dark ring
The evaporation rate of MG solution is 0.07037kg/ (m under border2H), the MG solution without any catalyst sample is in Xenon light shining
Water evaporation rate under penetrating is 1.05kg/ (m2H), CB/TiO is contained only2-xThe water evaporation rate of the MG solution of catalyst is
1.61kg/(m2H), water evaporation rate is compared to TiO in the presence of working as PC cone2-xCatalyst has more significant raising, water
Evaporation rate is 2.29kg/ (m2·h).More significantly work as CB/TiO2-xAfter the load of PC coning row, water evaporation rate can
Up to 4.53kg/ (m2H) it is greatly enhanced, this is mainly due to CB/TiO2-xIt is obtained with its compound rear absorbing properties of PC
To the enhancing for promoting and then resulting in photothermal conversion efficiency.(about 3 times of sunlights) CB/TiO under xenon source irradiation2-x/PC
Photothermal conversion efficiency according to formula calculated result be 93.52%.The present invention also uses CB/TiO2-x/ PC has done the correlation of processing salt
Experiment, in contrast, and has carried out the inspection of relevant ions concentration to the salt water before processing and the condensed water being collected into.
Demonstrate CB/TiO2-x/ PC has more excellent Driven by Solar Energy water evaporation water purification performance, as shown in figure 13.Using there are four types of tools
Leading ion (Na+, K+, Ca2+And Mg2+) salt water carry out desalination.It can be seen from the figure that all ions are all aobvious after desalination
The ion concentration for showing 4 orders of magnitude is successively decreased, and is reduced to 2.1mg/L hereinafter, being far below the drink of World Health Organization's defined
With these ion concentration standards in water, while also below the drinking water ion concentration standard of Environmental Protection Agency.Show CB/
TiO2-x/ PC has more excellent solar energy purifying water effect.
The good stability of catalyst is the major criterion that catalyst testing is had excellent performance, because having good circulation to stablize
Property is the necessary condition that catalyst is able to maintain permanent efficient catalytic performance and economic benefit.The present invention is to CB/TiO2-x/PC
Degradation MG solution photocatalysis stability is tested, and as shown in figure 14, discovery is right after it continues catalytic degradation 20 circulations
The degradation capability of pollutant MG is kept approximately constant, and change more by a small margin only occurs for degradation percentage, this shows CB/TiO2-x/
PC composite material has preferable catalytic stability, again demonstrates real using the method sprayed in PC three-dimensional structure after treatment
Existing CB/TiO2-xLoad on PC cone, have stronger binding force, while also for current powder catalyst in the application
The difficult problem of existing recycling provides a kind of ameliorative way, and has also further demonstrated that CB/TiO2-x/ PC composite material is in reality
A possibility that in the popularization and application of border.The present invention is also to CB/TiO2-xThe cyclical stability that/PC has carried out water evaporation performance carries out
Test finds CB/TiO as shown in figure 152-xAfter 20 water evaporation performance tests, water evaporation rate has small/PC
Fluctuation, and on the whole still keep stablizing, this shows CB/TiO2-x/ PC photothermal conversion aspect of performance has good stabilization
Property.
CB/TiO2-xThe efficient Water clarifying mechanism schematic diagram of/PC is as shown in figure 16, CB/TiO2-xPhotochemical catalyst is due to TiO2-xIt receives
Rice band structure, the presence of CB and Ti3+With the synergistic effect of the introducing of Lacking oxygen, more excellent photocatalysis performance is made it have.
When by CB/TiO2-xAfter PC poppet surface after being sprayed at PDA hydrophilic modifying, the CB/TiO of acquisition2-x/ PC composite material is entirely too
Very excellent light absorption is shown in sunlight spectral limit.During Driven by Solar Energy water evaporation, sufficient water supply is provided
And low-heat loss provides outstanding full spectral absorption for catalyst in the photocatalytic process.Therefore, this result sufficiently proves
CB/TiO2-x/ PC composite material not only has significant Driven by Solar Energy water evaporation performance, but also there is excellent light to urge
Change performance.CB/TiO2-xThe application of the efficient difunctional water purification performance of/PC composite material, it is single to have broken previous water purification material
The limitation of application provides new strategy to develop the water purification material of highly effective.
Claims (10)
1. a kind of three-dimensional structure loads TiO2-xThe preparation method of material, it is characterised in that the preparation method is in the steps below
It carries out:
Step 1: carbon black (CB) is added in Tris buffer (pH=8.5,50mM), it is ultrasonically treated 30min, and carry out to it
Stirring, is then added TiO2-x, continue to stir, after liquid to be mixed is uniform, the Dopamine hydrochloride mixing that concentration is 2mg/mL be added and stirs
It mixes uniformly, is subsequently placed in shaking table, be passed through air in concussion, handle 12h, be washed with deionized for several times, 60 DEG C of vacuum are dried
It is dry, obtain CB/TiO2-xPowder；
Step 2: with polycarbonate (PC) for raw material, 3D printing hollow cone successively carries out destressing, oil removal treatment, then
It is rinsed well with deionized water, then impregnates in dehydrated alcohol and handle 10min, it is 50mM's that concentration is directly transferred to after taking-up
In Tris-HCl buffer, Dopamine hydrochloride (2mg/mL) then is added, vacuum drying obtains PC cone；
Step 3: by step 1 CB/TiO2-xPowder is dissolved in organic solvent, ultrasonic treatment, configuration 10~20mg/mL concentration
CB/TiO2-xSuspension pours into suspension in spray gun, and at least 3 layers of even application in PC cone, are then rushed with deionized water
It washes, vacuum drying loads TiO to get to three-dimensional structure2-xThe preparation method of material.
2. a kind of three-dimensional structure loads TiO according to claim 12-xThe preparation method of material, it is characterised in that step 1 institute
State TiO2-xIt is prepared according to the following steps:
Step 1: taking 0.6gP25 to be dissolved in the NaOH solution that 60mL concentration is 10mol/L, be transferred to water heating kettle after ultrasonic 30min
In, then 12~48h of hydro-thermal process at 200 DEG C is washed with deionized water with the salt acid elution of 0.1M to pH value to 2.0 ± 0.2
It is washed repeatedly after washing repeatedly with dehydrated alcohol, dry 12h, is then placed in tube furnace, forges at 500 DEG C under 60 DEG C of vacuum conditions
4h is burnt, natually cooled to room temperature obtains white TiO2Nanobelt；
Step 2: taking white TiO made from 0.2g step 12Nanobelt is added 0.4g sodium borohydride, is fully ground uniformly mixed
Afterwards, it is put into tube furnace, in argon atmosphere, with 5 DEG C of min-1Heating rate be warming up to 300~450 DEG C, keep the temperature 3h, from
It is so cooled to room temperature, mixture is dissolved in deionized water, filter, wash, be dried in vacuo 12h at 70 DEG C, black TiO is made2-xIt receives
Rice band.
3. a kind of three-dimensional structure loads TiO according to claim 12-xThe preparation method of material, it is characterised in that in step 2
With 5 DEG C of min-1Heating rate be warming up to 360 DEG C.
4. a kind of three-dimensional structure loads TiO according to claim 12-xThe preparation method of material, it is characterised in that in step 1
CB and TiO2-xMass ratio be 1:(1~5), the ratio of CB mass and Tris buffer volume for (0.05~0.5) g:(10~
100) ratio of mL, CB mass and Dopamine hydrochloride volume is (2~10) g:1mL.
5. a kind of three-dimensional structure loads TiO according to claim 12-xThe preparation method of material, it is characterised in that in step 2
Specific step is as follows for 3D printing hollow cone: PC silk material being put into 60 DEG C of vacuum drying treatment 12h before printing, utilizes 3D
Max (3D Studio Max) software design goes out target print underlying structure, carries out printing behaviour after 3D printer identifies this file
Make, the nozzle diameter of printer is 0.4mm, and nozzle temperature is set as 250 DEG C~260 DEG C, and printing machine platform is set as 90 DEG C, room
Temperature is 80 DEG C, does not use any adhesive, and 1.75mm monofilament is sent into FDM printer, layer print speed by two pinch rollers
It is maintained at 1.5m/min, layer height is set as 0.05mm, and then successively printing, obtains hollow cone.
6. a kind of three-dimensional structure loads TiO according to claim 52-xThe preparation method of material, it is characterised in that spraying temperature
260 DEG C, fan opens ratio 60%, speed 20%.
7. the apex angle of hollow cone described in step 2 is 60 °~120 °.
8. a kind of three-dimensional structure loads TiO according to claim 12-xThe preparation method of material, it is characterised in that in step 2
12h is dried in vacuo at 45 DEG C.
9. a kind of three-dimensional structure loads TiO according to claim 12-xThe preparation method of material, it is characterised in that in step 3
Organic solvent is dehydrated alcohol, is dried in vacuo 4h at 30 DEG C.
10. a kind of three-dimensional structure loads TiO according to claim 12-xThe preparation method of material, it is characterised in that step 3
Middle 3 layers of spraying is in PC cone.
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| CN111211232A (en) * | 2020-03-15 | 2020-05-29 | 西北工业大学 | Preparation method of perovskite solar cell with dopamine chelated titanium dioxide |
| CN115044186A (en) * | 2022-07-15 | 2022-09-13 | 山东金宝电子股份有限公司 | Black resin glue solution, preparation method of prepreg, copper-clad plate and application |
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