CN102631919B - Preparation method of copper-titanium-oxide mesomorphism material - Google Patents

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

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CN102631919B
CN102631919B CN201210051111.6A CN201210051111A CN102631919B CN 102631919 B CN102631919 B CN 102631919B CN 201210051111 A CN201210051111 A CN 201210051111A CN 102631919 B CN102631919 B CN 102631919B
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copper
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titanium
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CN102631919A (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 preparation method of copper-titanium oxide mesomorphic material
Technical field
The invention belongs to the preparing technical field of functional material, specifically relate to the preparation method of copper-titanium oxide mesomorphic material.
Background technology
Functional material is the material that a large class has particular electrical, magnetic, light, sound, heat, chemistry and biological property, is the important foundation material of information technology, biotechnology, the contour frontier of energy technology and national defense construction.Recent years, the fast development of mesomorphic (mesocrystal) has caused chemist and the more concern of physicists.Especially for materials chemistry men, the mesomorphic microstructure due to them for the design of material provide 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 by surface, the polycrystalline that nano particle assembles.The sight crystal that is situated between is a kind of by the consistent crystalline state nano particle superstructure of the hundreds of nanometer orientation that even the special crystal face of hundreds of micron forms.The sight crystal that is situated between is also a kind of colloidal crystal with special crystal face that is made up of non-ball shaped unit.Therefore, compare the colloidal crystal being made up of ball shaped unit, it has the more free degree.The sight crystal that is situated between is only the pilot process forming in monocrystalline path conventionally.Mesomorphic, as the new kind of one of solid material, can regard the nanocrystal of crystallographic orientation assembling as.Mesomorphic special construction has brought many special natures, makes them in a lot of application, become the substitute of monocrystalline and polycrystalline (porous) material, and performance is better than 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, the people such as Fujishima delivered and have utilized TiO on Nature 2after the experimental result of semi-conductor electricity aurora decomposition water hydrogen making 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 stable chemical nature, catalytic activity are high, nontoxic, cheap, in the decontamination system application of the 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) wider, spectral response range is narrower, absorbing wavelength mainly concentrates on ultraviolet region (< 387nm).In the solar energy on arrival ground, the energy of this wave band is less than 5% still, and the ratio of visible light part accounts for 45% left and right of solar energy, lower for the utilization ratio of solar energy.In photocatalysis field, how to improve photocatalysis efficiency, the photochemical catalyst that can effectively absorb visible ray becomes the focus of a research.By the method compound with narrow gap semiconductor based on the most effective method of modifying of wide band gap semiconducter, 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 semiconductor can make photo-generated carrier be injected on another kind of semiconductor energy level by a kind of energy level of semiconductor grain, cause effective separation of charge, not only can effectively suppress the compound of light induced electron and hole, and expanded spectral response scope, therefore compound method is to improve a kind of effective way of conductor photocatalysis activity.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 ray.Work as TiO 2while 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 Einstein shift and can improve the utilization to solar energy.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and preparation method that a kind of copper-titanium oxide mesomorphic material is provided, the method can synthesize the variform copper-titanium oxide mesomorphic material different with band structure under conventional hydrothermal condition, its preparation technology is simple and easy to do, mild condition, prepared mesomorphic material spectral response range is wide, has good photocatalysis performance, under visible ray, under the process conditions of photocatalytic degradation of dye, within 60 minutes, degradation rate has reached more than 95%.
For achieving the above object, the present invention is achieved in that
A preparation method for copper-titanium oxide mesomorphic material, it is uniform dissolution in alcohol/water mixed solution by soluble metal mantoquita and titanium salt, continues and in alcohol/water mixed solution, carries out hydro-thermal reaction, after heat treatment obtains object product.
As a kind of preferred version, the present invention is uniform dissolution in alcohol/water mixed solution by soluble metal mantoquita and titanium salt, and adds surfactant in the process of mixing.
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 copper acetate.
Further, titanium salt of the present invention is one or more the mixture in butyl titanate, tetraisopropyl titanate or titanium acetylacetone.
Further, surfactant of the present invention is one or more the mixture in lauryl sodium sulfate, octadecylamine, glycerine-laurate, 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, isopropyl alcohol, and the volume ratio of alcohol and water is 1: 0.1～10.
Secondly, the molar concentration of soluble copper salt of the present invention and titanium salt is 0.01～2mol/L.
Again, the mol ratio of soluble copper salt of the present invention and titanium salt is 1: 0.2～5.
Hydrothermal temperature of the present 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, then after Muffle furnace is heat-treated, obtains object product; Described 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 features:
(1) the present invention has developed and has prepared copper-titanium oxide mesomorphic material new technology route, and this technique preparation cost is low, easy to control, has higher production efficiency, can realize industrial mass production.
(2) object product copper-titanium oxide mesomorphic material that prepared by the present invention, its purity is high, and impurity content is low, good dispersion, band structure can regulate and control, and can meet the requirement of photocatalytic applications field to visible light catalyst product.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the invention will be further described.Protection scope of the present invention is not only confined to the statement of following content.
Fig. 1 is the mesomorphic formation mechanism of copper-titanium oxide of the present invention schematic diagram;
Fig. 2 is copper-titanium oxide mesomorphic material X-ray diffractogram of the present invention;
Fig. 3 is Cu of the present invention 2o-TiO 2mesomorphic material SEM figure;
Fig. 4 is copper-titanium oxide mesomorphic material X-ray diffractogram 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 Induced Photocatalytic dye wastewater.
The specific embodiment
The present invention designs a kind of solution phase chemical method, thereby reaches a layering superstructure of link composition of copper-titanium oxide p-n by new chemistry route.The mesomorphic photocatalysis property of copper-titanium oxide can be assessed by the typical methyl orange of photocatalytic degradation.
The present invention is take soluble metal mantoquita and titanium salt as raw material, by mantoquita and titanium salt uniform dissolution in alcohol/water mixed solution according to a certain percentage, and add a certain amount of surfactant in the process of mixing, continue and in alcohol/water mixed solution, carry out hydro-thermal reaction (temperature is at 160～230 ℃, time is 6～48 hours), after filtering, wash, being dried, in Muffle furnace, heat-treat that (temperature is at 200～800 ℃, time is 2～48 hours), obtain copper-titanium oxide mesomorphic material.Preparation process of the present invention is:
(1) solubility cupric salt and titanium salt are all made into the alcohol water mixed solution of 0.01～2.0mol/L, at room temperature titanium salt is slowly added drop-wise in copper salt solution, stir and add surfactant simultaneously, the addition of surfactant is mole metering of mantoquita 1～10%, the addition of solubility titanium salt is pressed mantoquita/titanium salt=1: 0.2～5 molar ratio computing, and with 60～120 revs/min of mixing speed stirring reactions 5～30 minutes.
(2) by the mixed solution obtaining 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.
(3) hydro-thermal reaction finishes, and naturally cools to after room temperature, and the product that reaction is obtained is put into baking oven after filtering, and under 30～50 ℃ of conditions, dry 2～5 hours, makes Cu 2o-TiO 2mesomorphic material.
(4) by Cu 2o-TiO 2mesomorphic material is put into Muffle furnace and is heat-treated, and at 200～800 ℃, under condition, heat treatment 2～48 hours, makes CuO-TiO 2mesomorphic material.
(5) utilize prepared Cu-Ti oxide mesomorphic material as photochemical catalyst (0.5g/L), the methyl orange solution of degraded 30mg/L.In photocatalysis experiment, light source used is 500W halogen tungsten lamp (simulated solar irradiation).Before irradiation, the methyl orange solution that contains catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye change in concentration.
Fig. 1 is the mesomorphic formation mechanism of copper-titanium oxide of the present invention schematic diagram.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 copper-titanium oxide mesomorphic material X-ray diffractogram of the present invention, and wherein # represents the diffraction maximum of titanium dioxide, and * represents the diffraction maximum of cuprous oxide.Fig. 4 is copper-titanium oxide mesomorphic material X-ray diffractogram of the present invention, and wherein # represents the diffraction maximum of titanium dioxide, and ^ represents the diffraction maximum of cupric oxide.Fig. 6 is the prepared Cu2O-TiO of the present invention 2mesomorphic material and the CuO-TiO2 mesomorphic material photocatalysis efficiency figure in Visible Light Induced Photocatalytic dye wastewater.A catalyst-free; B Cu 2o-TiO 2mesomorphic material; C CuO-TiO 2mesomorphic material.
Shown in Fig. 2～5, copper-titanium oxide mesomorphic material of preparing gained is carried out to X-ray diffraction analysis (XRD) in the present invention and ESEM (SEM) is analyzed.Fig. 6 is prepared mesomorphic material photocatalysis performance resolution chart.
Embodiment 1
Be that 0.1mol/L copper chloride alcohol water mixed solution is slowly added drop-wise to the butyl titanate alcohol water mixed solution that concentration is 0.1mol/L by concentration, in mixed process, add octadecylamine.Wherein alcohol water mixed solution is second alcohol and water according to v: v=1: 1 preparation, copper chloride/butyl titanate=0.2: 1 molar ratio computing, octadecylamine is copper chloride 1% (mole), with 70 revs/min of mixing speed stirring reactions 20 minutes.The mixed solution obtaining is carried out to 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, the product that reaction is obtained filters after washing, puts into baking oven, under 40 ℃ of conditions, dry 4 hours, obtains Cu 2o-TiO 2mesomorphic material (Fig. 2 and Fig. 3).By Cu 2o-TiO 2mesomorphic material is put into Muffle furnace and is heat-treated, and under 600 ℃ of conditions, heat treatment 5 hours, makes CuO-TiO 2mesomorphic material (Fig. 4 and Fig. 5).
Utilize prepared Cu-Ti oxide mesomorphic material as photochemical catalyst (0.5g/L), the methyl orange solution of degraded 30mg/L.In photocatalysis experiment, light source used is 500W halogen tungsten lamp (simulated solar irradiation).Before irradiation, the methyl orange solution that contains catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye change in concentration.As shown in Figure 6, the degradation rate of 60 minutes is that the degradation rate of 95%, 120 minute is 100%.
Embodiment 2
Be that 0.1mol/L copper nitrate alcohol water mixed solution is slowly added drop-wise to the butyl titanate alcohol water mixed solution that concentration is 0.1mol/L by concentration, in mixed process, add octadecylamine.Wherein alcohol water mixed solution is second alcohol and water according to v: v=1: 1 preparation, copper nitrate/butyl titanate=0.2: 1 molar ratio computing, octadecylamine is copper nitrate 1% (mole), with 70 revs/min of mixing speed stirring reactions 20 minutes.The mixed solution obtaining is carried out to 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, the product that reaction is obtained filters after washing, puts into baking oven, under 40 ℃ of conditions, dry 4 hours, obtains Cu 2o-TiO 2mesomorphic material.By Cu 2o-TiO 2mesomorphic material is put into Muffle furnace and is heat-treated, and under 600 ℃ of conditions, heat treatment 5 hours, makes CuO-TiO 2mesomorphic material.
Utilize prepared Cu-Ti oxide mesomorphic material as photochemical catalyst (0.5g/L), the methyl orange solution of degraded 30mg/L.In photocatalysis experiment, light source used is 500W halogen tungsten lamp (simulated solar irradiation).Before irradiation, the methyl orange solution that contains catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye change in concentration.The degradation rate of 60 minutes is that the degradation rate of 97%, 120 minute is 99.9%.
Embodiment 3
Be that 0.1mol/L copper nitrate alcohol water mixed solution is slowly added drop-wise to the butyl titanate alcohol water mixed solution that concentration is 0.1mol/L by concentration, in mixed process, add lauryl sodium sulfate.Wherein alcohol water mixed solution is second alcohol and water according to v: v=1: 1 preparation, copper nitrate/butyl titanate=0.2: 1 molar ratio computing, lauryl sodium sulfate is copper nitrate 2% (mole), with 70 revs/min of mixing speed stirring reactions 20 minutes.The mixed solution obtaining is carried out to 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, the product that reaction is obtained filters after washing, puts into baking oven, under 40 ℃ of conditions, dry 3 hours, obtains Cu 2o-TiO 2mesomorphic material.By Cu 2o-TiO 2mesomorphic material is put into Muffle furnace and is heat-treated, and under 600 ℃ of conditions, heat treatment 5 hours, makes CuO-TiO 2mesomorphic material.
Utilize prepared Cu-Ti oxide mesomorphic material as photochemical catalyst (0.5g/L), the methyl orange solution of degraded 30mg/L.In photocatalysis experiment, light source used is 500W halogen tungsten lamp (simulated solar irradiation).Before irradiation, the methyl orange solution that contains catalysis material stirs 30 minutes in the dark, carries out illumination after reaching adsorption equilibrium.By spectrophotometric determination methyl orange dye change in concentration.The degradation rate of 60 minutes is that the degradation rate of 96%, 120 minute approaches 100%.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (1)

1. the preparation method of copper-titanium oxide mesomorphic material, it is characterized in that: the uniform dissolution in alcohol/water mixed solution by soluble metal mantoquita and titanium salt, and in the process of mixing, add surfactant, continue and in alcohol/water mixed solution, carry out hydro-thermal reaction and after heat treatment obtain object product; Described soluble copper salt is one or more the mixture in copper chloride, copper sulphate, copper nitrate or copper acetate; Described titanium salt is one or more the mixture in butyl titanate, tetraisopropyl titanate or titanium acetylacetone; Described surfactant is one or more the mixture in lauryl sodium sulfate, octadecylamine, glycerine-laurate, polyethylene glycol; Alcohol in described alcohol/water mixed solution is one or more the mixture in methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, and the volume ratio of alcohol and water is 1: 0.1～10; The molar concentration of described soluble copper salt and titanium salt is 0.01～2 mol/L; The mol ratio of described soluble copper salt and titanium salt is 1: 0.2～5; Described hydrothermal temperature is at 160～230 ℃, and the reaction time is 6～48 hours; In alcohol/water mixed solution, carry out hydro-thermal reaction, then after Muffle furnace is heat-treated, obtain object product; Described Muffle furnace heat treatment temperature is at 200～800 ℃, and the time is 2～48 hours.
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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
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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
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