CN102631919A - Preparation method of copper-titanium-oxide mesomorphism material - Google Patents

Preparation method of copper-titanium-oxide mesomorphism material Download PDF

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CN102631919A
CN102631919A CN2012100511116A CN201210051111A CN102631919A CN 102631919 A CN102631919 A CN 102631919A CN 2012100511116 A CN2012100511116 A CN 2012100511116A CN 201210051111 A CN201210051111 A CN 201210051111A CN 102631919 A CN102631919 A CN 102631919A
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copper
titanium
alcohol
titanium oxide
mesomorphic
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CN102631919B (en
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许家胜
张�杰
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Bohai University
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Abstract

The invention belongs to the technical field of function materials and relates to a preparation method of a copper-titanium-oxide mesomorphism material. The preparation method comprises the following steps of: uniformly dissolving soluble metallic copper slat and titanium salt in a mixed solution of alcohol/water according to a certain proportion, and adding a certain quantity of surfactant in the mixing process; performing hydrothermal reaction, filtering, washing, drying in the mixed solution of alcohol/water continually; and then performing thermal treatment in a muffle furnace to obtain the copper-titanium-oxide mesomorphism material. According to the preparation method, the technology is simple and convenient, the purity of the prepared material is high, the content of impurities is low, the preparation cost of the material is low, the performance of the material is excellent, and thus the material can be subjected to industrialized mass production. The copper-titanium-oxide mesomorphism material prepared by the method can serve as a photochemical catalyst responsive to visible light, and has wide application prospect in the fields of degradation of dyeing waste water and indoor harmful gas, photochemical catalysis disinfection and the like.

Description

The mesomorphic preparation methods of copper-titanium oxide
Technical field
The invention belongs to the preparing technical field of functional material, specifically relate to the mesomorphic preparation methods of copper-titanium oxide.
Background technology
Functional material is the material that a big class has particular electrical, magnetic, light, sound, heat, chemistry and biological property, is the important foundation material of high frontier such as information technology, biotechnology, energy technology and national defense construction.Recent years, the fast development of mesomorphic (mesocrystal) has caused chemist and physicists' more concern.Especially for the materials chemistry men; Mesomorphic because their microstructure is that the design of material provides new opportunity (referring to
Figure BDA0000139558130000011
H; Antonietti M.Mesocrystals and nonclassical crystallization; John Wiley&Sons, New York 2008.; Song R;
Figure BDA0000139558130000012
H.Mesocrystals-ordered nanoparticle superstructures.Adv.Mater.; 2010; 22,1301-1330.).Mesomorphic (be situated between and see the abbreviation of crystal, non-traditional crystallization) is not the monocrystalline that growth forms, and is can adsorb the polycrystalline that nano particle assembles through the surface.The sight crystal that is situated between is a kind of consistent crystalline state nano particle superstructure of being made up of hundreds of nanometer even the special crystal face of hundreds of micron of orientation.The sight crystal that is situated between also is a kind of colloidal crystal with special crystal face that is made up of non-ball shaped unit.Therefore, compare the colloidal crystal that is made up of ball shaped unit, it has the more freedom degree.The sight crystal that is situated between only is the pilot process that forms in the monocrystalline path usually.Mesomorphic, as a kind of new kind of solid material, can regard the nanocrystal of crystallographic orientation assembling as.Mesomorphic special construction has brought many special natures, makes them in plurality of applications, become the substitute of monocrystalline and polycrystalline (porous) material, and performance is superior to them, particularly in the application of catalysis, sensing and power conversion (referring to
Figure BDA0000139558130000013
H; Antonietti M.Mesocrystals:inorganic superstructures made by highly parallel crystallization and controlled alignment.Angew.Chem.Int.Ed.; 2005,44,5576-559 1.;
Figure BDA0000139558130000014
H, MannS.Higher-order organization by mesoscale self-assembly and transformation of hybrid nanostructures.Angew.Chem.Int.Ed., 2003,42,2350-2365.; Zhou L, Smyth-Boyle D, O ' Brien P.A facile synthesis of uniform NH 4TiOF 3Mesocrystals and their conversion to TiO 2Mesocrystals.J.Am.Chem.Soc., 2008,130,1309-1320).
1972, people such as Fujishima delivered on Nature and have utilized TiO 2After semi-conductor electricity aurora decomposition water is produced the experimental result of hydrogen and oxygen; The research of conductor photocatalysis has started upsurge very soon (referring to Honda K; Fujishima A.Electrochemical photolysis of water at a semiconductor electrode.Nature; 1972,238,37-38.; Thompson T, Yate J.Surface science studies of the photoactivation of TiO 2New photochemical processes.Chem.Rev., 2006,106,4428-4453.).TiO in numerous semiconductor light-catalysts 2Because of advantages such as its chemical property are stable, catalytic activity is high, nontoxic, cheap, in the decontamination system application of different pollutants of degraded and eliminating bacteria, be considered to have most the catalysis material of exploitation potential quality.But TiO 2Energy gap (3.2eV) broad, spectral response range is narrower, absorbing wavelength mainly concentrate on ultraviolet region (＜387nm).In the solar energy that arrives ground, the energy of this wave band is less than 5% still, and the ratio of visible light part accounts for about 45% of solar energy, and is lower for the utilization ratio of solar energy.In photocatalysis field, how to improve photocatalysis efficiency, the photochemical catalyst that can effectively absorb visible light becomes the focus of a research.Based on wide band gap semiconducter the most effectively method of modifying be through with the narrow gap semiconductor composite methods; So-called composite semiconductor is the compound system of two or more certain microstructure that semiconductor forms, and the more single semiconductor of its physical property can change.The meaning of composite semiconductor is to have the semiconductive particles of different level structures; Utilize low-gap semiconductor sensitization wide bandgap semiconductor; Utilize two kinds of energy level differences between the semiconductor that photo-generated carrier is injected on the another kind of semiconductor energy level by a kind of energy level of semiconductor grain; Caused effective separation of charge; Not only can suppress the compound of light induced electron and hole effectively, and expand the spectral response scope, so composite methods is to improve the active a kind of effective way of conductor photocatalysis.The oxide of copper (comprises CuO and Cu 2O) be two kinds of semi-conducting materials with the narrow p type that can be with, they can directly absorb visible light.Work as TiO 2When being combined into the nano composite material of copper-titanium oxide with the oxide of copper, this narrow bandgap structure semiconductor can absorb more long wavelength's light, makes absorption spectrum red shift and can improve the utilization to solar energy.
Summary of the invention
The present invention is intended to overcome the weak point of prior art and provides a kind of copper-titanium oxide mesomorphic preparation methods, and this method can synthesize the mesomorphic material of the variform copper-titanium oxide different with band structure under the hydrothermal condition of routine, and its preparation technology is simple and easy to do; Mild condition; Prepared mesomorphic material spectrum response range is wide, has good photocatalysis performance, under visible light; Under the process conditions of photocatalytic degradation of dye, degradation rate had reached more than 95% in 60 minutes.
For achieving the above object, the present invention is achieved in that
The mesomorphic preparation methods of a kind of copper-titanium oxide, it continues soluble metal mantoquita and titanium salt uniform dissolution in alcohol/water mixed solution in alcohol/water mixed solution, to carry out hydro-thermal reaction, after heat treatment promptly gets the purpose product.
As a kind of preferred version, the present invention is soluble metal mantoquita and titanium salt uniform dissolution in alcohol/water mixed solution, and in the process of mixing, adds surfactant.
As another kind of preferred version, soluble copper salt of the present invention is one or more the mixture in copper chloride, copper sulphate, copper nitrate or the copper acetate.
Further, titanium salt according to the invention is one or more the mixture in butyl titanate, tetraisopropyl titanate or the titanium acetylacetone.
Further, surfactant according to the invention is one or more the mixture in lauryl sodium sulfate, octadecylamine, glycerine-laurate, the polyethylene glycol.
In addition, the alcohol of alcohol/water mixed solution of the present invention in being is one or more the mixture in methyl alcohol, ethanol, ethylene glycol, the isopropyl alcohol, and the volume ratio of alcohol and water is 1: 0.1～10.
Secondly, the molar concentration of soluble copper salt according to the invention and titanium salt is 0.01～2mol/L.
Once more, the mol ratio of soluble copper salt according to the invention and titanium salt is 1: 0.2～5.
Hydrothermal temperature according to the invention is at 160～230 ℃, and the reaction time is 6～48 hours.
The present invention carries out hydro-thermal reaction in alcohol/water mixed solution, after Muffle furnace is heat-treated, promptly get the purpose product then; Said Muffle furnace heat treatment temperature is at 200～800 ℃, and the time is 2～48 hours.
Compared with prior art, the present invention has following characteristics:
(1) the present invention has developed the mesomorphic material new technology route of preparation copper-titanium oxide, and this prepared cost is low, easy to control, has higher production efficiency, can realize industrial mass production.
(2) the mesomorphic material of purpose product copper-titanium oxide of the present invention's preparation, its purity is high, and impurity content is low, good dispersion, band structure can be regulated and control, and can satisfy the photocatalytic applications field to the visible light catalyst requirement of products.
Description of drawings
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is described further.Protection scope of the present invention not only is confined to the statement of following content.
Fig. 1 is the mesomorphic formation mechanism of a copper-titanium oxide of the present invention sketch map;
Fig. 2 is the mesomorphic material X-ray diffractogram of copper-titanium oxide of the present invention;
Fig. 3 is Cu of the present invention 2O-TiO 2Mesomorphic material SEM figure;
Fig. 4 is the mesomorphic material X-ray diffractogram of copper-titanium oxide of the present invention;
Fig. 5 is CuO-TiO of the present invention 2Mesomorphic material SEM figure;
Fig. 6 is the prepared Cu of the present invention 2O-TiO 2Mesomorphic material and CuO-TiO 2The photocatalysis efficiency figure of mesomorphic material in visible light degradation of dye sewage.
The specific embodiment
The present invention designs a kind of solution phase chemistry method, thereby forms a layering superstructure through the link that new chemistry route reaches copper-titanium oxide p-n.The mesomorphic photocatalysis property of copper-titanium oxide can be assessed through the typical dyestuff methyl orange of photocatalytic degradation.
The present invention is a raw material with soluble metal mantoquita and titanium salt, with mantoquita and titanium salt uniform dissolution in alcohol/water mixed solution according to a certain percentage, and in the process of mixing, adds certain amount of surfactant; Continue and in alcohol/water mixed solution, carry out hydro-thermal reaction (temperature is at 160～230 ℃; Time is 6～48 hours), after filtration, washing, the drying, heat-treat in Muffle furnace that (temperature is at 200～800 ℃; Time is 2～48 hours), promptly obtain the mesomorphic material of copper-titanium oxide.Preparation process of the present invention is:
(1) solubility cupric salt and titanium salt all are made into the pure water mixed solution of 0.01～2.0mol/L; At room temperature slowly be added drop-wise to titanium salt in the copper salt solution; Stir and add surfactant simultaneously; The addition of surfactant was the mole metering of mantoquita 1～10%, and the addition of solubility titanium salt is pressed the molar ratio computing of mantoquita/titanium salt=1: 0.2～5, with 60～120 rev/mins of mixing speed stirring reactions 5～30 minutes.
(2) at a certain temperature, carry out hydro-thermal reaction, hydrothermal temperature is at 160～230 ℃ of C, and the hydro-thermal reaction time is 6～48 hours with the mixed solution that obtains.
(3) hydro-thermal reaction finishes, naturally cool to room temperature after, put into baking oven after the product that reaction is obtained filters, under 30～50 ℃ of conditions, dry 2～5 hours, promptly make Cu 2O-TiO 2Mesomorphic material.
(4) with Cu 2O-TiO 2Mesomorphic material is put into Muffle furnace and is heat-treated, and at 200～800 ℃, under the condition, heat treatment 2～48 hours promptly makes CuO-TiO 2Mesomorphic material.
(5) utilize the mesomorphic material of prepared Cu-Ti oxide as photochemical catalyst (0.5g/L), the methyl orange solution of degraded 30mg/L.Used light source is 500W halogen tungsten lamp (simulated solar irradiation) in the photocatalysis experiment.Before the irradiation, the methyl orange solution that contains catalysis material stirred 30 minutes in the dark, carried out illumination after reaching adsorption equilibrium.With spectrophotometric determination methyl orange dye change in concentration.
Fig. 1 is the mesomorphic formation mechanism of a copper-titanium oxide of the present invention sketch map.Be assembled into Cu by cuprous oxide and titanium dioxide nano-particle 2O/TiO 2Mesomorphic material, and be transformed into CuO/TiO 2Mesomorphic material.Fig. 2 is the mesomorphic material X-ray diffractogram of copper-titanium oxide of the present invention, and wherein # representes the diffraction maximum of titanium dioxide, and * representes the diffraction maximum of cuprous oxide.Fig. 4 is the mesomorphic material X-ray diffractogram of copper-titanium oxide of the present invention, and wherein # representes the diffraction maximum of titanium dioxide, and ^ representes the diffraction maximum of cupric oxide.Fig. 6 is the prepared Cu2O-TiO of the present invention 2The photocatalysis efficiency figure of the mesomorphic material of mesomorphic material and CuO-TiO2 in visible light degradation of dye sewage.The A catalyst-free; B Cu 2O-TiO 2Mesomorphic material; C CuO-TiO 2Mesomorphic material.
Shown in Fig. 2～5, the mesomorphic material of copper-titanium oxide that the present invention will prepare gained carries out X-ray diffraction analysis (XRD) and ESEM (SEM) analysis.Fig. 6 is prepared mesomorphic material light catalysis property resolution chart.
Embodiment 1
With concentration is that 0.1mol/L copper chloride alcohol water mixed solution slowly is added drop-wise to the butyl titanate alcohol water mixed solution that concentration is 0.1mol/L, adds octadecylamine in the mixed process.Wherein pure water mixed solution is the second alcohol and water according to v: v=1: 1 preparation, the molar ratio computing of copper chloride/butyl titanate=0.2: 1, octadecylamine was 1% (mole) of copper chloride, with 70 rev/mins of mixing speed stirring reactions 20 minutes.The mixed solution that obtains is carried out hydro-thermal reaction, and hydrothermal temperature is at 180 ℃, and the hydro-thermal reaction time is 24 hours.After hydro-thermal reaction finishes, naturally cool to room temperature, after the product that reaction is obtained filters washing, put into baking oven, under 40 ℃ of conditions, dry 4 hours, obtain Cu 2O-TiO 2Mesomorphic material (Fig. 2 and Fig. 3).With Cu 2O-TiO 2Mesomorphic material is put into Muffle furnace and is heat-treated, and under 600 ℃ of conditions, heat treatment 5 hours promptly makes CuO-TiO 2Mesomorphic material (Fig. 4 and Fig. 5).
Utilize the mesomorphic material of prepared Cu-Ti oxide as photochemical catalyst (0.5g/L), the methyl orange solution of degraded 30mg/L.Used light source is 500W halogen tungsten lamp (simulated solar irradiation) in the photocatalysis experiment.Before the irradiation, the methyl orange solution that contains catalysis material stirred 30 minutes in the dark, carried out illumination after reaching adsorption equilibrium.With spectrophotometric determination methyl orange dye change in concentration.As shown in Figure 6,60 minutes degradation rate is that 95%, 120 minute degradation rate is 100%.
Embodiment 2
With concentration is that 0.1mol/L copper nitrate alcohol water mixed solution slowly is added drop-wise to the butyl titanate alcohol water mixed solution that concentration is 0.1mol/L, adds octadecylamine in the mixed process.Wherein pure water mixed solution is the second alcohol and water according to v: v=1: 1 preparation, the molar ratio computing of copper nitrate/butyl titanate=0.2: 1, octadecylamine was 1% (mole) of copper nitrate, with 70 rev/mins of mixing speed stirring reactions 20 minutes.The mixed solution that obtains is carried out hydro-thermal reaction, and hydrothermal temperature is at 180 ℃, and the hydro-thermal reaction time is 24 hours.After hydro-thermal reaction finishes, naturally cool to room temperature, after the product that reaction is obtained filters washing, put into baking oven, under 40 ℃ of conditions, dry 4 hours, obtain Cu 2O-TiO 2Mesomorphic material.With Cu 2O-TiO 2Mesomorphic material is put into Muffle furnace and is heat-treated, and under 600 ℃ of conditions, heat treatment 5 hours promptly makes CuO-TiO 2Mesomorphic material.
Utilize the mesomorphic material of prepared Cu-Ti oxide as photochemical catalyst (0.5g/L), the methyl orange solution of degraded 30mg/L.Used light source is 500W halogen tungsten lamp (simulated solar irradiation) in the photocatalysis experiment.Before the irradiation, the methyl orange solution that contains catalysis material stirred 30 minutes in the dark, carried out illumination after reaching adsorption equilibrium.With spectrophotometric determination methyl orange dye change in concentration.60 minutes degradation rate is that 97%, 120 minute degradation rate is 99.9%.
Embodiment 3
With concentration is that 0.1mol/L copper nitrate alcohol water mixed solution slowly is added drop-wise to the butyl titanate alcohol water mixed solution that concentration is 0.1mol/L, adds lauryl sodium sulfate in the mixed process.Wherein pure water mixed solution is the second alcohol and water according to v: v=1: 1 preparation, the molar ratio computing of copper nitrate/butyl titanate=0.2: 1, lauryl sodium sulfate was 2% (mole) of copper nitrate, with 70 rev/mins of mixing speed stirring reactions 20 minutes.The mixed solution that obtains is carried out hydro-thermal reaction, and hydrothermal temperature is at 160 ℃, and the hydro-thermal reaction time is 48 hours.After hydro-thermal reaction finishes, naturally cool to room temperature, after the product that reaction is obtained filters washing, put into baking oven, under 40 ℃ of conditions, dry 3 hours, obtain Cu 2O-TiO 2Mesomorphic material.With Cu 2O-TiO 2Mesomorphic material is put into Muffle furnace and is heat-treated, and under 600 ℃ of conditions, heat treatment 5 hours promptly makes CuO-TiO 2Mesomorphic material.
Utilize the mesomorphic material of prepared Cu-Ti oxide as photochemical catalyst (0.5g/L), the methyl orange solution of degraded 30mg/L.Used light source is 500W halogen tungsten lamp (simulated solar irradiation) in the photocatalysis experiment.Before the irradiation, the methyl orange solution that contains catalysis material stirred 30 minutes in the dark, carried out illumination after reaching adsorption equilibrium.With spectrophotometric determination methyl orange dye change in concentration.60 minutes degradation rate is that 96%, 120 minute degradation rate is near 100%.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. the mesomorphic preparation methods of copper-titanium oxide is characterized in that: with soluble metal mantoquita and titanium salt uniform dissolution in alcohol/water mixed solution, continue and in alcohol/water mixed solution, carry out hydro-thermal reaction and after heat treatment promptly get the purpose product.
2. the mesomorphic preparation methods of copper-titanium oxide according to claim 1 is characterized in that: with soluble metal mantoquita and titanium salt uniform dissolution in alcohol/water mixed solution, and in the process of mixing, add surfactant.
3. the mesomorphic preparation methods of copper-titanium oxide according to claim 2 is characterized in that: said soluble copper salt is one or more the mixture in copper chloride, copper sulphate, copper nitrate or the copper acetate.
4. the mesomorphic preparation methods of copper-titanium oxide according to claim 3 is characterized in that: said titanium salt is one or more the mixture in butyl titanate, tetraisopropyl titanate or the titanium acetylacetone.
5. the mesomorphic preparation methods of copper-titanium oxide according to claim 4 is characterized in that: said surfactant is one or more the mixture in lauryl sodium sulfate, octadecylamine, glycerine-laurate, the polyethylene glycol.
6. the mesomorphic preparation methods of copper-titanium oxide according to claim 5; It is characterized in that: the alcohol in described alcohol/water mixed solution is one or more the mixture in methyl alcohol, ethanol, ethylene glycol, the isopropyl alcohol, and the volume ratio of alcohol and water is 1: 0.1～10.
7. the mesomorphic preparation methods of copper-titanium oxide according to claim 6 is characterized in that: the molar concentration of said soluble copper salt and titanium salt is 0.01～2mol/L.
8. the mesomorphic preparation methods of copper-titanium oxide according to claim 7 is characterized in that: the mol ratio of said soluble copper salt and titanium salt is 1: 0.2～5.
9. according to the mesomorphic preparation methods of arbitrary described copper-titanium oxide of claim 1～8, it is characterized in that: said hydrothermal temperature is at 160～230 ℃, and the reaction time is 6～48 hours.
10. the mesomorphic preparation methods of copper-titanium oxide according to claim 9 is characterized in that: in alcohol/water mixed solution, carry out hydro-thermal reaction, after Muffle furnace is heat-treated, promptly get the purpose product then; Said Muffle furnace heat treatment temperature is at 200～800 ℃, and the time is 2～48 hours.
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CN102910609A (en) * 2012-11-12 2013-02-06 渤海大学 Preparation method of microcrystal with dumbbell feature and zinc phosphate grade structure
CN103466693A (en) * 2013-09-29 2013-12-25 安徽工业大学 Copper titanate nanoneedle and preparation method thereof
CN106861693A (en) * 2017-04-07 2017-06-20 中国科学院过程工程研究所 A kind of copper based composite metal oxidate mesomorphic material and its production and use
CN108654207A (en) * 2018-05-17 2018-10-16 沈阳理工大学 A kind of preparation method of multi-functional water treatment ceramsite filter
CN109650442A (en) * 2019-01-14 2019-04-19 北京科技大学 A kind of preparation method of Copper-cladding Aluminum Bar barium oxide mesomorphic dusty material
CN113600213A (en) * 2021-06-21 2021-11-05 北京工商大学 Copper-based oxide/phosphide composite mesomorphic material and preparation method and application thereof
CN113952954A (en) * 2021-11-25 2022-01-21 白银新大孚科技化工有限公司 Composite material and preparation method thereof

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102910609A (en) * 2012-11-12 2013-02-06 渤海大学 Preparation method of microcrystal with dumbbell feature and zinc phosphate grade structure
CN102910609B (en) * 2012-11-12 2014-12-10 渤海大学 Preparation method of microcrystal with dumbbell feature and zinc phosphate grade structure
CN103466693A (en) * 2013-09-29 2013-12-25 安徽工业大学 Copper titanate nanoneedle and preparation method thereof
CN103466693B (en) * 2013-09-29 2014-09-03 安徽工业大学 Copper titanate nanoneedle and preparation method thereof
CN106861693A (en) * 2017-04-07 2017-06-20 中国科学院过程工程研究所 A kind of copper based composite metal oxidate mesomorphic material and its production and use
CN106861693B (en) * 2017-04-07 2019-07-05 中国科学院过程工程研究所 A kind of copper based composite metal oxidate mesomorphic material and its preparation method and application
CN108654207A (en) * 2018-05-17 2018-10-16 沈阳理工大学 A kind of preparation method of multi-functional water treatment ceramsite filter
CN109650442A (en) * 2019-01-14 2019-04-19 北京科技大学 A kind of preparation method of Copper-cladding Aluminum Bar barium oxide mesomorphic dusty material
CN113600213A (en) * 2021-06-21 2021-11-05 北京工商大学 Copper-based oxide/phosphide composite mesomorphic material and preparation method and application thereof
CN113600213B (en) * 2021-06-21 2022-04-22 北京工商大学 Copper-based oxide/phosphide composite mesomorphic material and preparation method and application thereof
CN113952954A (en) * 2021-11-25 2022-01-21 白银新大孚科技化工有限公司 Composite material and preparation method thereof

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