CN1556151A - Preparation method of photocatulyzed active bromine adulerated titanium dioxide nano-material - Google Patents
Preparation method of photocatulyzed active bromine adulerated titanium dioxide nano-material Download PDFInfo
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- CN1556151A CN1556151A CNA2003101098437A CN200310109843A CN1556151A CN 1556151 A CN1556151 A CN 1556151A CN A2003101098437 A CNA2003101098437 A CN A2003101098437A CN 200310109843 A CN200310109843 A CN 200310109843A CN 1556151 A CN1556151 A CN 1556151A
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Abstract
A Br doped nano TiO2 material with photocatyletic activity is prepared by introducing Br to TiO2 crystal. It contains Ti (48-73 wt.%), O (26.9-42) and Br (0.1-10). Its energy gap can be triggered by visual light, so realizing full-frequency absorption of visual light and increasing the light quantum efficiency of TiO2 material.
Description
Technical Field
The invention relates to a preparation method of a nano material, in particular to a preparation method of a photocatalytic active bromine-doped titanium dioxide nano material, belonging to the field of inorganic nano photocatalytic materials.
Background
The titanium dioxide semiconductor photocatalytic oxidation technology is a novel modern technology. Because it can widely use natural energy-solar energy, and has the outstanding characteristics of low energy consumption, mild reaction condition, simple operation, capability of reducing secondary pollution and the like, it is increasingly paid attention to, and has wide application prospect. In recent years, semiconductor photocatalysis has become one of the research hotspots in the fields of photochemistry and environmental protection, and the application of the semiconductor photocatalysis in wastewater treatment has been reported in many documents. A large number of researches prove that dyes, surfactants, organic halides, pesticides, cyanides, phenols, polychlorinated biphenyls, polycyclic aromatic hydrocarbons and the like can be effectively catalyzed, degraded, decolorized, detoxified and mineralized into inorganic small molecular substances, so that the pollution to the environment is eliminated. In practical applications, TiO2The photocatalytic material has been used in the fields of water and air purification devices, self-cleaning glass surfaces, antibacterial photocatalytic ceramic tiles and the like, and has produced great economic, environmental and social benefits.
TiO2The forbidden band width of the light absorption band is 3.2eV, and the light absorption range is limited to the ultraviolet region (the wavelength is less than 380 nm). But thepart of light can not reach 5 percent of the total energy of the sunlight irradiating the ground, and the TiO is used for the current2The quantum efficiency is not higher than 28% at most, so the utilization efficiency of solar energy is only about 1%, and the utilization of solar energy is greatly limited. How to solve TiO2Dependence on Ultraviolet (UV) (4.5% in sunlight), modifying the catalyst to red shift its photoresponse wavelength to visible region (46% in sunlight radiation), so that it can directly use the sunlight radiation, and is TiO2The key point of the photocatalytic oxidation technology is entering the practical stage. And TiO 22The catalyst is not high in activity, and is deactivated because excited valence band holes and conduction band electrons generated after being irradiated by light are easy to recombine. According to the third law of thermodynamics, all physical systems have different degrees of irregularity except at absolute zero degrees. The actual crystal is of an approximate space lattice structure and always has one or more structural defects. When traces of impurities are incorporated into the crystal, impurity defects may form, the presence of these defects acting as photocatalyst TiO2The activity plays an important role.
The literature search shows that the preparation method of the bromine-doped titanium dioxide nano material is irrelevant.
Disclosure of Invention
Objects of the invention
Provides a preparation method of a bromine-doped titanium dioxide nano material with photocatalytic activity. The forbidden band width is reduced to the extent of utilizing visible light range (400-> 800nm) by a simpler preparation process so as to improve the light quantum efficiency. Meanwhile, the preparation method has the advantages of simple production and preparation process and low production cost.
The invention is realized by the following technical scheme that a bromine doping technology is adopted to synthesize a bromine doping modified titanium dioxide nano material, bromine is doped into crystal lattices of titanium dioxide crystals, and the bromine is doped into crystal gaps of the titanium dioxide crystals, wherein the bromine doping modified titanium dioxide nano material comprises the following 3 elements in percentage by weight: the content of titanium is 54.55-59.90%; the oxygen content is 35.45-40.00%; the bromine content is 0.10% -10.00%.
Such doping will act as follows for the catalyst:
① the p orbital of bromine atom and the 2p orbital of O atom form new molecular orbitals after hybridization, while TiO2The valence band of (A) is basically composed of the 2p orbital of an O atom, the p orbital of a bromine atom and the 2p orbital of an O atom form a new molecular orbital after hybridization, the energy of which is higher than that of the 2p orbital of the original O atom, and TiO2The height of the conduction band is not changed, thereby reducing TiO2The forbidden band width of the solar energy collector enables the light absorption of the solar energy collector to be red-shifted to the whole visible light region, and the visible light part in solar light radiation can be directly utilized.
② impurities are introduced into the crystal to cause defects, which can effectively capture photo-generated electrons, inhibit the recombination of electrons and holes, prolong the service life of holes, and improve the photocatalytic activity of titanium dioxide.
The invention is further described in detail below, comprising the steps of:
(a) adding a titanium precursor into a proper amount of bromine dopant aqueous solution, and fully and uniformly mixing to generate a white precipitate;
(b) the precursor of the titanium is inorganic salt or titanium alkoxide of titanium. If the precursor of the titanium is inorganic salt of the titanium, the white precipitate is washed by deionized water until the concentration of other anions (such as chloride ions and sulfate ions) is less than 0.5mg/L, then the white precipitate is filtered, and the precipitate washed by the deionized water is collected, and if the precursor of the titanium is titanium alkoxide, the treatment is not needed;
(c) drying the white precipitate at a certain temperature, and grinding to obtain solid powder;
(d) and carrying out heat treatment on the solid powder, and calcining the solid powder in an air atmosphere at the temperature of 300-700 ℃ to obtain the bromine-doped titanium dioxide nano material.
The titanium precursor comprises titanium alkoxide and inorganic titanium salt, wherein the titanium alkoxide comprises one or a combination of tetrabutyl titanate, isopropyl titanate and ethyl titanate; the inorganic salt of titanium is one or two of titanium chloride, titanium sulfate and the like.
The bromine doping agent is: HBr, Br2、HBrO3Or a bromine-containing salt.
The drying time from the white precipitate to the solid dried substance is not less than 20 minutes, and the drying temperature is not more than 200 ℃. The white precipitate is dried by direct heating or natural drying. The optimal drying temperature is 100-150 ℃, the optimal drying time is 2-12 hours, and the optimal drying mode is direct heating drying.
The solid powder heat treatment has the temperature rise speed of 1-40 ℃/min, the heat preservation time of0.5-6 hours and the temperature reduction speed of 10-40 ℃/min. The optimal temperature rising speed is 2-20 ℃/min, the optimal heat preservation time is 0.5-3 hours, and the optimal temperature reduction speed is 15-30 ℃/min.
The bromine-doped titanium dioxide nano catalyst material is in an anatase type or coexists in the anatase type and the rutile type. The bromine-doped titanium dioxide nano catalyst material has the forbidden bandwidth which can be excited by the irradiation of visible light, thereby realizing the full-frequency absorption of the visible light,therefore, the modified TiO can be obviously improved2The photon efficiency of the material. The light source can be natural light, artificial simulated sunlight or ultraviolet light source.
The method for preparing the bromine-doped titanium dioxide nano material with high catalytic activity under visible light comprises the steps of adding a small amount of bromine dopant into water to prepare an aqueous solution of the bromine dopant, then dropwise adding a precursor solution of titanium into the aqueous solution to generate a white precipitate, drying the white precipitate for 2-10 hours under the condition of direct heating and drying at 100-150 ℃ to remove water, then grinding to obtain solid powder, then carrying out heat treatment on the solid powder, calcining in an air atmosphere at 300-700 ℃ to form a crystal form, and finally cooling to room temperature to obtain the bromine-doped titanium dioxide nano catalyst material.
The photocatalytic activity test of the bromine-doped titanium dioxide nano material is characterized by catalyzing and degrading phenol in water by the bromine-doped titanium dioxide nano material under the irradiation of visible light. Phenol is an organic matter with strong toxicity, and the waste water containing phenol is a pollutant with wide source and serious harm, and is widely existed in thewaste water of industries such as steel, petrochemical industry, plastics, synthetic fibers, urban gas and the like, and the pollution problem caused by the waste water is more and more prominent. Therefore, the present invention selects it as a simulated polluting compound. The photocatalytic oxidative decomposition of phenol is based on the following chemical reactions: the photocatalytic activity experiment of degrading phenol in water under the catalysis of the bromine-doped titanium dioxide nano material is carried out at normal temperature and normal pressure by using a 1000 ml photocatalytic reactor. The process for measuring the photocatalytic activity of the bromine-doped titanium dioxide nano material comprises the following steps: weighing 500 ml of prepared 20mg/L phenol solution, adding into a photocatalytic reactor, adding 0.35 g of accurately weighed bromine-doped titanium dioxide nano material, and stirring by strong magnetic force. Phenol and bromine in the reactor were doped with dioxygen before the photocatalytic experimentThe titanium nano material reaches the adsorption balance. The initial concentration of phenol in the reactor after equilibrium adsorption was reached was about 19mg/L, which remained constant until the 1000W xenon lamp (with a 420nm filter) was turned on. Reactor with a reactor shellThe initial temperature of the inner part was 25. + -. 1 ℃. In order to keep the temperature in the reactor constant, a circulating water cooling device is arranged outside the reactor. In the reaction process, strong magnetic stirring is always adopted in the reactor. The phenol concentration was measured by 4-aminoantipyrine spectrophotometry, and the change in phenol concentration was measured by sampling every 20 minutes after the reaction. The phenol concentration gradually decreases with the progress of the photocatalytic reaction, and the degradation reaction is a first-order reaction, which conforms to the first-order reaction kinetic equation 1n (C)0/Ct)＝kt，C0As initial phenol concentration, CtK is the first order reaction kinetic apparent rate constant for the phenol concentration at which the reaction proceeded to t. The prepared bromine-doped titanium dioxide nanomaterial and titanium dioxide powder (model P25, Degussa, Germany) were each tested for catalytic oxidation activity in this way.
The invention has substantive characteristics and remarkable progress. The bromine-doped titanium dioxide nano material prepared by the preparation method has a forbidden bandwidth which can be excited by visible light irradiation, realizes full-frequency absorption of visible light, and has high photon efficiency; meanwhile, the preparation method is simple and has the prospect of industrial production.
Drawings
Fig. 1 is a graph comparing uv-vis absorption spectra of a bromine-doped titanium dioxide nanomaterial with high catalytic activity under visible light and a titanium dioxide powder (model P25, Degussa, germany). The measuring instrument is a VARIAN Cary 500 UV-vis spectrophotometer.
Detailed Description
In order to confirm the light absorption performance of the bromine-doped titanium dioxide nano powder catalyst with high catalytic activity in visible light, an ultraviolet-visible absorption spectrum was measured. The measuring instrument is a VARIAN Cary 500 UV-visspectrophotometer. The weight percentages of 3 elements in the bromine-doped titanium dioxide nano material of the following examples are all selected according to the following ranges: the titanium accounts for 54.55 to 59.90 percent, the oxygen accounts for 35.45 to 40.00 percent, and the bromine accounts for 0.10 to 10.00 percent.
Example 1
15ml of bromine aqueous solution (3 percent by weight) and 10ml of tetrabutyl titanate (more than 98.0 percent by weight) are reacted until white precipitate is completely generated. The white precipitate was directly heated in an oven, treated at 120 ℃ for 8 hours, and evaporated to remove water and alcohol substances produced in the reaction to obtain a solid dried product. And grinding the obtained solid dried substance to ensure that the particles are uniform and soft agglomeration is reduced. Grinding and putting into a muffle furnaceAnd calcining the mixture for 2 hours at 320 ℃ to obtain the bromine-doped titanium dioxide nano catalyst material with high catalytic activity under visible light. In a catalytic activity test, the apparent rate constant k of the first-order reaction kinetics of the catalyst material for catalyzing and degrading phenol is 6.86 multiplied by 10-3min-1The first order kinetic apparent rate constant k is 1.04X 10 for titanium dioxide powder (P25, Degussa)-3min-16.6 times of the amount of the bromine-doped titanium dioxide nanomaterial with high catalytic activity under visible light is formed after 2 hours of heat treatment.
The ultraviolet-visible absorption spectrum of the bromine-doped titanium dioxide nano material with high catalytic activity and the titanium dioxide powder (P25, Degussa) is shown in figure 1, and the bromine-doped titanium dioxide nano catalyst material and the titanium dioxide powder (P25, Degussa) have the same strong light absorption in the ultraviolet region; in the visible light region, the light absorption of the bromine-doped titanium dioxide nano-catalyst material is obviously higher than that of titanium dioxide powder (P25, Degussa). This is attributed to the bromine doping technique red-shifting the photoresponse wavelength into the visible region, enhancing the absorption of visible light.
Example 2
15ml of bromine aqueous solution (3 percent by weight) and 10ml of titanium sulfate (more than 40.0 percent by weight) are reacted until white precipitate is completely generated. After rinsing the resulting white precipitate with deionized water, the resulting solution was washed until the anion (sulfate ion) concentration was less than 0.5 mg/L. Then filtered and the precipitated material washed with deionized water was collected. Heating the white precipitate in an oven, treating at 120 deg.C for 8 hr, evaporating to remove water and reaction productThe crude alcohol material yielded a solid dry. And grinding the solid dried substance to make the particles uniform and reduce soft agglomeration. Then placing the titanium dioxide nano material in a muffle furnace, and calcining the titanium dioxide nano material for 2 hours at 350 ℃ to obtain the bromine-doped titanium dioxide nano material with high catalytic activity under visible light. In a catalytic activity test, the apparent rate constant k of the first-order reaction kinetics of the catalyst material for catalyzing and degrading phenol is 5.41 multiplied by 10-3min-1The first order kinetic apparent rate constant k is 1.04X 10 for titanium dioxide powder (P25, Degussa)-3min-15.2 times of the total weight of the powder. It can be seen that after 2 hours of heat treatment, a bromine-doped titanium dioxide nanomaterial with high catalytic activity under visible light is formed.
Example 3
10ml of hydrogen bromide solution (2mol/L) was reacted with 10ml of tetrabutyl titanate (mass% content>98.0%) until a white precipitate was completely formed. The white precipitate was directly heated in an oven, treated at 120 ℃ for 8 hours, and evaporated to remove waterand alcohol substances produced in the reaction to obtain a solid dried product. And grinding the obtained solid dried substance to ensure that the particles are uniform and soft agglomeration is reduced. And (3) placing the mixture into a muffle furnace after grinding, and calcining the mixture for 2 hours at 350 ℃ to obtain the bromine-doped titanium dioxide nano material with high catalytic activity under visible light. In a catalytic activity test, the apparent rate of the first-order reaction kinetics of the catalyst material for catalyzing and degrading phenol is alwaysNumber k is 5.72 × 10-3min-1The first order kinetic apparent rate constant k is 1.04X 10 for titanium dioxide powder (P25, Degussa)-3min-15.5 times of the total weight of the powder. It can be seen that after 2 hours of heat treatment, a bromine-doped titanium dioxide nanomaterial with high catalytic activity under visible light is formed.
Example 4
15ml of hydrogen bromide solution (2mol/L) was reacted with 10ml of tetrabutyl titanate (mass% content>98.0%) until a white precipitate was formed completely. The white precipitate was directly heated in an oven, treated at 120 ℃ for 8 hours, and evaporated to remove water and alcohol substances produced in the reaction to obtain a solid dried product. And grinding the obtained solid dried substance to ensure that the particles are uniform and soft agglomeration is reduced. After grindingAnd putting the mixture into a muffle furnace, and calcining the mixture for 1 hour, 2 hours and 3 hours at the temperature of 320 ℃ respectively to obtain the bromine-doped titanium dioxide nano material with high catalytic activity under visible light. In a catalytic activity test, the apparent rate constant of the first-order reaction kinetics of the catalyst material for catalyzing and degrading phenol is 4.53 multiplied by 10-3min-1、6.06×10-3min-1，5.97×10-3min-1Are all superior to titanium dioxide powder (P25, Degussa) in that the first-order reaction kinetic apparent rate constant k is 1.04X 10-3min-1. It can be seen that after heat treatment, a bromine-doped titanium dioxide nanomaterial with high catalytic activity under visible light is formed.
Claims (9)
1. A preparation method of a photocatalytic active bromine-doped titanium dioxide nano material is characterized in that a bromine doping technology is adopted to synthesize a bromine-doped modified titanium dioxide nano material, bromine is doped into crystal lattices of titanium dioxide crystals, and bromine is doped into crystal gaps of the titanium dioxide crystals, and the weight percentage of 3 elements in the bromine-doped titanium dioxide nano material is as follows: the content of titanium is 54.55-59.90%; the oxygen content is 35.45-40.00%; the bromine content is 0.10% -10.00%.
2. The process for the preparation of photocatalytically active bromine-doped titanium dioxide nanomaterial according to claim 1, characterized in that the process of the present invention is further defined as follows, the process comprising the specific steps of:
(a) adding a titanium precursor into a proper amount of bromine dopant aqueous solution, and fully and uniformly mixing to generate a white precipitate;
(b) if the precursor of the titanium is inorganic salt of the titanium, washing the titanium precursor with deionized water after generating a white precipitate until the concentration of other anions is less than 0.5mg/L, then filtering, and collecting the precipitate washed with the deionized water, wherein if the precursor of the titanium is titanium alkoxide, the washing treatment is not needed;
(c) drying the white precipitate at a certain temperature, and grinding to obtain a solid dried substance;
(d) and (3) carrying out heat treatment on the solid dried substance, and calcining the solid dried substance in an air atmosphere at the temperature of 300-700 ℃ to obtain the bromine-doped titanium dioxide nano material.
3. The method for producing a photocatalytically active bromine-doped titanium dioxide nanomaterial according to claim 1 or 2, wherein the produced bromine-doped titanium dioxide nanomaterial is in an anatase form or coexists in an anatase form and a rutile form, and bromine is doped in both crystal lattices and crystal gaps of the titanium dioxide crystal material.
4. The method for preparing a bromine-doped titanium dioxide nanomaterial with photocatalytic activity according to claim 1 or 2, wherein the bromine-doped titanium dioxide nanomaterial has catalytic activity under both visible light and ultraviolet light, and the light source used in the method can be natural light, artificial simulated sunlight or ultraviolet light.
5. The method of claim 2, wherein the titanium precursor comprises titanium alkoxide and inorganic titanium salt, wherein the titanium alkoxide comprises one or a combination of tetrabutyl titanate, isopropyl titanate and ethyl titanate; the inorganic salt of titanium is one or two of titanium chloride and titanium sulfate.
6. The process for the preparation of photocatalytically active bromine-doped titanium dioxide nanomaterial according to claim 2The method is characterized in that the bromine doping agentis as follows: HBr, Br2、HBrO3Or a bromine-containing salt.
7. The process for producing photocatalytically active bromine-doped titanium dioxide nanomaterial according to claim 2, wherein the drying time of the white precipitate to a solid dried substance is 20 minutes or more and the drying temperature is 200 ℃ or less.
8. The process according to claim 2 or 7, wherein the white precipitate is dried by direct heating or natural drying.
9. The method for preparing the photocatalytically active bromine-doped titanium dioxide nanomaterial according to claim 2, wherein the temperature rise rate of the heat treatment is 1-40 ℃/min, the heat preservation time is 0.5-6 hours, and the temperature drop rate is 15-40 ℃/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326620C (en) * | 2005-08-25 | 2007-07-18 | 上海交通大学 | Process for preparing bromine blended metal oxide catalyst |
| CN104607212A (en) * | 2013-11-04 | 2015-05-13 | 天津大学 | Method for preparing bromine deposition rutile type titanium dioxide, and applications of bromine deposition rutile type titanium dioxide |
| CN106423227A (en) * | 2016-10-31 | 2017-02-22 | 天津大学 | Synthesis method of Br-doped TiO2 hollow spherical nanomaterial |
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2003
- 2003-12-30 CN CN 200310109843 patent/CN1257943C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326620C (en) * | 2005-08-25 | 2007-07-18 | 上海交通大学 | Process for preparing bromine blended metal oxide catalyst |
| CN104607212A (en) * | 2013-11-04 | 2015-05-13 | 天津大学 | Method for preparing bromine deposition rutile type titanium dioxide, and applications of bromine deposition rutile type titanium dioxide |
| CN106423227A (en) * | 2016-10-31 | 2017-02-22 | 天津大学 | Synthesis method of Br-doped TiO2 hollow spherical nanomaterial |
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