CN105800679A - Method for preparing TiO2 spherical three-level hierarchical structure - Google Patents

Method for preparing TiO2 spherical three-level hierarchical structure Download PDF

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CN105800679A
CN105800679A CN201610130114.7A CN201610130114A CN105800679A CN 105800679 A CN105800679 A CN 105800679A CN 201610130114 A CN201610130114 A CN 201610130114A CN 105800679 A CN105800679 A CN 105800679A
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spherical
tio
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CN105800679B (en
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祝名伟
刘玉容
陈延峰
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Nanjing University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/04Oxides; Hydroxides
    • C01G23/047Titanium dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

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Abstract

The invention discloses a method for preparing a TiO2 spherical three-level hierarchical structure. The method comprises the following steps of: (1) uniformly mixing Ti2O nano-particles, other metal oxide nano-particles and polyethylene glycol by a ball-milling method to obtain mixed powder of Ti2O and other metal oxide nano-particles and polyethylene glycol; (2) preparing slurry by utilizing the powder, uniformly stirring, and drying to obtain a film or bulk material on the substrate; (3) calcining to remove organic matters to obtain a spherical two-level hierarchical structure formed by the TiO2 nano-particles and other metal oxide nano-particles; and (4) removing other metal oxide nano-particles from the spherical two-level hierarchical structure to obtain the TiO2 spherical three-level hierarchical structure. The preparation method disclosed by the invention is low in cost and easy to operate, does not have pollution, can be used for large-scale quick production, and has wide application in the fields of photocatalysis, sensing, pollution regulation, self-cleaning coating and the like.

Description

A kind of TiO2The preparation method of spherical three grades of hierarchies
Technical field
The present invention relates to a kind of TiO2The preparation method of spherical three grades of hierarchies, belongs to Nano/micron fine structure material extremely technology of preparing.
Background technology
The preparation of the spherical hierarchy of metal-oxide and the regulation and control of progression thereof are technology with important application background.Such as pass through in titanium dioxide, add a certain proportion of ferrum oxide and can improve its photocatalytic activity, the color of film coating can be controlled by adding the ferrum oxide of different content, because the Superhydrophilic of material itself, therefore can be used as decoration and self-cleaning coating;The spherical complex of titanium dioxide and zinc oxide or stannum oxide can be used as the material of semiconductor transducer.
The complex of multi-component can the performance advantage of comprehensive each constituent element, realize performance enhancement and application is wider, spherical structure is not changed additionally by the regulation and control to its progression, complete maintain spherical structure advantage, make it at photoelectric field, waste gas wastewater treatment, the aspect such as self-cleaning coating is widely used.
Summary of the invention
It is an object of the invention to provide a kind of easily operated, with low cost TiO2The preparation method of spherical three grades of hierarchies.
Spherical three grades of hierarchies of the present invention are to be made up of following structure: by TiO2The nano-TiO formed after removing other metal-oxide in the micron-size spherical structure of granule composition, micron-size spherical structure2Structure, nano-TiO2The nanostructured of granule itself.This TiO2The preparation method of spherical three grades of hierarchies comprises the following steps:
(1) by TiO2Nano-particle, other metal oxide nanoparticles and the Polyethylene Glycol method mix homogeneously by ball milling, it is thus achieved that TiO2Mixed-powder with other metal oxide nanoparticles and Polyethylene Glycol;
(2) utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;
(3) calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy that nano-particle and other metal oxide nanoparticles are constituted;
(4) utilize the method dissolved or react to remove other metal oxide nanoparticles described from spherical secondary hierarchy, namely obtain TiO2Spherical three grades of hierarchies.
Described TiO2Nano particle diameter is 2~100 nanometers, and other metal oxide nanoparticles particle diameter is 2-100 nanometer.
Other described metal-oxide is one or several combinations in ferrum oxide, nickel oxide, copper oxide, silver oxide, magnesium oxide, zinc oxide or stannum oxide.
The present invention compared with prior art, has the advantage that (1) provides a kind of novel preparation method preparing nano-metal-oxide multilevel hierarchy;(2) content ratio that can pass through to regulate and control each metal-oxide prepares material requested easily;(3) the inventive method is while keeping spherical structure, it is achieved that the regulation and control to complex progression;(4) technique is easily operated, it is not necessary to complicated equipments and devices, cost is low;(5) pollution-free, high production, can high-volume quickly produce, in photocatalysis, sensing, pollution control, the field such as self-cleaning coating is widely applied.
Accompanying drawing explanation
Fig. 1 is titanium dioxide and mixes prepared spherical secondary hierarchy with the Zinc oxide nanoparticle of 10%;
Fig. 2 is the TiO obtained after being removed by Zinc oxide nanoparticle2Spherical three grades of hierarchies.
Detailed description of the invention
Embodiment 1:
By the TiO that the grain diameter of mass ratio 1:0.02 is 2 nanometers2Nano-particle and the ferric oxide nanometer particle mixing that particle diameter is 2 nanometers, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with ferric oxide nanometer particle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;At 450 DEG C, calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy of nano-particle and ferric oxide nanometer particle.By dissolving with hydrochloric acid, ferric oxide nanometer particle is removed in reaction, it is thus achieved that TiO2Spherical three grades of hierarchies.
Embodiment 2:
By the TiO that the grain diameter of mass ratio 1:0.04 is 100 nanometers2Nano-particle and the nickel oxide nanoparticle mixing that particle diameter is 100 nanometers, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with nickel oxide nanoparticle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;At 450 DEG C, calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy of nano-particle and nickel oxide nanoparticle.Dissolved by dilute sulfuric acid and remove nickel oxide nanoparticle, it is thus achieved that TiO2Spherical three grades of hierarchies.
Embodiment 3:
By the TiO that mass ratio 1:0.1 grain diameter is 30 nanometers2Nano-particle and the Zinc oxide nanoparticle mixing that particle diameter is 20 nanometers, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with Zinc oxide nanoparticle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;At 450 DEG C, calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy of nano-particle and Zinc oxide nanoparticle.Above-mentioned Zinc oxide nanoparticle is removed, it is thus achieved that TiO by hydrochloric acid reaction2Spherical three grades of hierarchies.
Embodiment 4:
Be 1:0.06 grain diameter by mass ratio it is the TiO of 50 nanometers2Nano-particle and the copper oxide nanometer particle mixing that particle diameter is 60 nanometers, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with copper oxide nanometer particle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;At 450 DEG C, calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy of nano-particle and copper oxide nanometer particle.Above-mentioned copper oxide nanometer particle is removed, it is thus achieved that TiO by sulfuric acid dissolution, reaction etc.2Spherical three grades of hierarchies.
Embodiment 5:
Be 1:0.08 grain diameter by mass ratio it is the TiO of 40nm2Nano-particle and the magnesium oxide nanoparticle mixing that grain diameter is 80 nanometers, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with magnesium oxide nanoparticle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;Organic substance is calcined away, it is thus achieved that the spherical secondary hierarchy of TiO2 nano-particle and magnesium oxide nanoparticle at 450 DEG C.Above-mentioned magnesium oxide nanoparticle is removed, it is thus achieved that TiO by dissolving with hydrochloric acid, reaction2Spherical three grades of hierarchies.
Embodiment 6:
Be 1:0.15 grain diameter by mass ratio it is the TiO of 100nm2Nano-particle and the silver oxide nano-particle mixing that grain diameter is 70 nanometers, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with silver oxide nano-particle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;Organic substance is calcined away, it is thus achieved that TiO at 450 DEG C2The spherical secondary hierarchy of nano-particle and silver oxide nano-particle.Above-mentioned silver oxide nano-particle is removed, it is thus achieved that TiO by dissolving with hydrochloric acid, reaction2Spherical three grades of hierarchies.
Embodiment 7:
By the TiO2 nano-particle of mass ratio to be 1:0.2 grain diameter be 100nm and silver oxide nano-particle mixing that grain diameter is 100 nanometers; then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000 again, it is thus achieved that the mixed-powder of TiO2 and silver oxide nano-particle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;Organic substance is calcined away, it is thus achieved that the spherical secondary hierarchy of TiO2 nano-particle and silver oxide nano-particle at 450 DEG C.Above-mentioned silver oxide nano-particle is removed, it is thus achieved that spherical three grades of hierarchies of TiO2 by dissolving with hydrochloric acid, reaction.
Embodiment 8:
By zinc oxide that grain diameter is 30nm and ferric oxide nanometer particle mixing, it is 1:0.1 by TiO that grain diameter is 30 nanometers according to mass ratio2Nano-particle and said mixture mixing, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with zinc oxide, ferric oxide nanometer particle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;At 450 DEG C, calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy of nano-particle and zinc oxide and ferric oxide nanometer particle.Above-mentioned zinc oxide and ferric oxide nanometer particle is removed, it is thus achieved that TiO by dissolving with hydrochloric acid2Spherical three grades of hierarchies.
Embodiment 9:
By magnesium oxide that particle diameter is 50 nanometers and tin oxide nanoparticles mixing, it is 1:0.05 by TiO that grain diameter is 40 nanometers according to mass ratio2Nano-particle and said mixture mixing, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with magnesium oxide, tin oxide nanoparticles and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;At 450 DEG C, calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy of nano-particle and magnesium oxide and tin oxide nanoparticles.Above-mentioned magnesium oxide and tin oxide nanoparticles is removed, it is thus achieved that TiO by dissolving with hydrochloric acid, reaction etc.2Spherical three grades of hierarchies.
Embodiment 10:
It is the zinc oxide of 30nm, ferrum oxide and magnesium oxide nanoparticle mixing by grain diameter, is 1:0.2 by TiO that grain diameter is 50 nanometers according to mass ratio2Nano-particle and said mixture mixing, then mixed homogeneously by the method for ball milling according to the mass ratio of 3:1 with the Polyethylene Glycol of molecular weight 20000, it is thus achieved that TiO again2Mixed-powder with zinc oxide, ferrum oxide, magnesium oxide nanoparticle and Polyethylene Glycol;Utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;At 450 DEG C, calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy of nano-particle and magnesium oxide nanoparticle.Above-mentioned zinc oxide, ferrum oxide and magnesium oxide nanoparticle is removed, it is thus achieved that TiO by dissolving with hydrochloric acid, reaction2Spherical three grades of hierarchies.

Claims (4)

1. a TiO2The preparation method of spherical three grades of hierarchies, it is characterised in that comprise the following steps:
(1) by TiO2Nano-particle, other metal oxide nanoparticles and the Polyethylene Glycol method mix homogeneously by ball milling, it is thus achieved that TiO2Mixed-powder with other metal oxide nanoparticles and Polyethylene Glycol;
(2) utilize above-mentioned powder preparation slurry, stir, on substrate, obtain thin film or bulk after drying;
(3) calcining removes Organic substance, it is thus achieved that TiO2The spherical secondary hierarchy that nano-particle and other metal oxide nanoparticles are constituted;
(4) from spherical secondary hierarchy, remove other metal oxide nanoparticles described, namely obtain TiO2Spherical three grades of hierarchies.
2. a kind of TiO according to claim 12The preparation method of spherical three grades of hierarchies, it is characterised in that described TiO2Nano particle diameter is 2~100 nanometers, and other metal oxide nanoparticles particle diameter described is 2-100 nanometer.
3. a kind of TiO according to claim 12The preparation method of spherical three grades of hierarchies, it is characterised in that other described metal-oxide is one or several combinations in ferrum oxide, nickel oxide, copper oxide, silver oxide, magnesium oxide, zinc oxide or stannum oxide.
4. a kind of TiO according to claim 1,2 or 32The preparation method of spherical three grades of hierarchies, it is characterised in that in described step (4), removes the method for other metal oxide nanoparticles described for dissolving or reaction.
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Cited By (4)

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CN107603425A (en) * 2017-09-25 2018-01-19 常州市协旺纺织品有限公司 A kind of preparation method of Superhydrophilic coating
CN108097181A (en) * 2017-12-19 2018-06-01 东北大学 A kind of method and product for preparing indium oxide shell structure
CN109225222A (en) * 2017-07-11 2019-01-18 中国科学院上海硅酸盐研究所 A kind of composite photo-catalyst and its application
CN110308184A (en) * 2019-06-21 2019-10-08 冉圳 A kind of preparation method of high sensitivity ethanol-sensing material

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109225222A (en) * 2017-07-11 2019-01-18 中国科学院上海硅酸盐研究所 A kind of composite photo-catalyst and its application
CN109225222B (en) * 2017-07-11 2021-03-16 中国科学院上海硅酸盐研究所 Composite photocatalyst and application thereof
CN107603425A (en) * 2017-09-25 2018-01-19 常州市协旺纺织品有限公司 A kind of preparation method of Superhydrophilic coating
CN108097181A (en) * 2017-12-19 2018-06-01 东北大学 A kind of method and product for preparing indium oxide shell structure
CN108097181B (en) * 2017-12-19 2020-05-19 东北大学 Method for preparing indium oxide shell structure and product
CN110308184A (en) * 2019-06-21 2019-10-08 冉圳 A kind of preparation method of high sensitivity ethanol-sensing material

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