CN1555913A - Preparaton method of photo catalytic active nitrogen adulterated titanium dioxide nano material - Google Patents
Preparaton method of photo catalytic active nitrogen adulterated titanium dioxide nano material Download PDFInfo
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Abstract
A nitrogen doped nano-class TiO2material with photocatalytic activity is prepared by doping N into TiO2 crystal. It features that its energy gap can be triggered by visual light, realizing the full-frequency absorption to visual light for increasing its light quantum efficiency.
Description
Technical Field
The invention relates to a preparation method of a nano material, in particular to a preparation method of a nitrogen-doped titanium dioxide nano material with photocatalytic activity, belonging to the field of inorganic nano photocatalytic materials.
Background
Titanium dioxide (TiO)2) The 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 the part of light can not reach 5 percent of the total energy of sunlight irradiating the ground, and TiO2The 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 substitution defects may form, the presence of these defects being attributable to photocatalytic TiO2The activity plays an important role.
Found by literature search, Chinese patent publication numbers are: CN 1454710, patent name: a titanium dioxide photocatalysis film containing nitrogen and a preparation method thereof, which discloses a preparation method of a titanium dioxide material subjected to nitridation treatment, and the patent is as follows: in the reaction gas of the mixed gas of high-purity oxygen and nitrogen, the titanium dioxide photocatalysis film containing nitrogen is prepared by adopting a magnetron sputtering method. The patent claims that the forbidden band width of the semiconductor photocatalyst is reduced, so that the film has the absorption capacity to visible light, has the catalytic degradation capacity to organic pollutants under the irradiation of the visible light, and has greatly improved degradation capacity compared with a pure titanium dioxide photocatalytic film under the irradiation of ultraviolet light. However, the magnetron sputtering process is complex and the equipment is expensive, so the cost for preparing the titanium dioxide photocatalytic film containing nitrogen is high, and the titanium dioxide photocatalytic film can not be used on a large scale.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a nitrogen-doped titanium dioxide nano material with photocatalytic activity. The method is used for preparing TiO through a simpler preparation process2The forbidden band width is reduced to the extent of the available visible light range (400-800nm) by doping nitrogen, so as to improve the light quantum efficiency. The preparation method has the advantages of simplifying production and preparation processes and reducing production cost.
The invention is realized by the following technical scheme that the nitrogen-doped modified titanium dioxide nano material is synthesized by adopting a nitrogen-doping technology, nitrogen elements are doped in crystal lattices of titanium dioxide crystals, and the nitrogen elements are doped in crystal gaps of the titanium dioxide crystals, wherein the weight percentage of 3 elements in the nitrogen-doped titanium dioxide nano material is as follows: the content of titanium accounts for 60.01 to 60.20 percent; the oxygen content accounts for 36.8% -39.89%; the content of nitrogen is 0.10-3.00%.
Such doping will act as follows for the catalyst:
① the p orbital of nitrogen atom and the 2p orbital of O atom are hybridized to form new molecular orbital, and TiO2Is essentially the 2p orbital of the O atomFormed by hybridization of the p orbital of nitrogen atom and the 2p orbital of O atom to form a new molecular orbital, 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 or defects are caused, which can effectively capture photo-generated electrons, inhibit the recombination of electron-hole, prolong the service life of hole, and improve the photo catalytic 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 aqueous solution of nitrogen dopant, 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 required to be washed by deionized water after being generated until the concentration of 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 required;
(c) drying the white precipitate at a certain temperature, and then 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 nitrogen-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 nitrogen dopant is as follows: NH (NH)4OH，CO(NH2)2Ammonia gas (NH)3) And the like, ammonia derived substances and ammonium salts.
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 5-10 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 of 0.5-6 hours and the temperature reduction speed of 15-40 ℃/min. The optimal temperature rising speed is 3-10 ℃/min, the optimal heat preservation time is 0.5-3 hours, and the optimal temperature reduction speed is 20-30 ℃/min.
The nitrogen-doped titanium dioxide catalyst nano material is in an anatase type or coexists in the anatase type and the rutile type. The nitrogen-doped titanium dioxide catalyst nano material has a forbidden band width which can be excited by visible light irradiation, so that the full-frequency absorption of visible light is realized, and 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 preparation method of the nitrogen-doped titanium dioxide catalyst nanomaterial with high catalytic activity under visible light comprises the steps of adding a small amount of nitrogen dopant into water to prepare a water solution of the nitrogen dopant, dropwise adding the water solution into a precursor solution of titanium to generate a white precipitate, drying the white precipitate for 2-10 hours at 100-150 ℃ under the condition of direct heating and drying to remove water, grinding to obtain solid powder, performing heat treatment on the solid powder, calcining at 300-700 ℃ in air atmosphere to form a crystal form, and finally cooling to room temperature to obtain the nitrogen-doped titanium dioxide catalyst nanomaterial.
The photocatalytic activity test of the nitrogen-doped titanium dioxide catalyst nanomaterial is characterized by decomposing phenol in water by the nitrogen-doped titanium dioxide catalyst nanomaterial 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 the waste water of industries such as steel, petrochemical industry, plastics, synthetic fiber and urban gas, etc., and the pollution problem caused by the waste water is more and more seriousThe more prominent the disease is. Therefore, the present invention selects it as a simulated polluting compound. Photocatalysis of phenolOxidative decomposition is based on the following chemical reaction: the photocatalytic activity experiment of the nitrogen-doped titanium dioxide catalyst nanomaterial for decomposing phenol in water 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 nitrogen-doped titanium dioxide catalyst 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 nitrogen-doped titanium dioxide catalyst nano material, and stirring by strong magnetic force. Before the photocatalysis experiment, phenol and the nitrogen-doped titanium dioxide catalyst nano material in the reactor reach 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. The initial temperature in the reactor 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 along with the progress of the photocatalytic reaction, and the degradation reaction is a first-order reaction and conforms to a first-order reaction kinetic equation ln (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 nitrogen-doped titanium dioxide catalyst nano material and titanium dioxide powder (P25 type, Degussa company in Germany) are used for measuring the catalytic oxidation activity by the method.
The invention has substantive characteristics and remarkable progress. The fluorine-doped titanium dioxide nano catalyst material prepared by the preparation method has forbidden bandwidth which can be excited by visible light irradiation, realizes full-frequency absorption of visible light, and can remarkably improve the modified TiO2The photon efficiency of the material; meanwhile, the preparation method is simple and has the prospect of industrial production.
Drawings
FIG. 1 is a graph comparing UV-visible absorption spectra of nitrogen-doped titanium dioxide nanopowder catalyst of high catalytic activity and titanium dioxide powder (P25 type, Degussa, Germany). The measuring instrument is a VARIAN Cary 500UV-vis spectrophotometer.
Detailed Description
In order to confirm the light absorption performance of the nitrogen-doped titanium dioxide nano powder catalyst having high catalytic activity in visible light, ultraviolet-visible absorption spectrum (UV-Vis) was measured. The measuring instrument is a VARIAN Cary 500UV-vis spectrophotometer. The weight percentages of 3 elements in the nitrogen-doped titanium dioxide nano powder of the following examples are all selected according to the following ranges: the titanium accounts for 60.01 to 60.20 percent, the oxygen accounts for 36.8 to 39.89 percent, and the nitrogen accounts for 0.10 to 3.00 percent.
Example 1
20ml of nitrogen aqueous solution (0.5M/L) was reacted with 20ml of tetrabutyl titanate (mass percent>98.0%) until a white precipitate was completely formed. Heating the white precipitate in oven directly, treating at 120 deg.C for 4 hr, evaporating to remove water and part of alcohol substances generated in reaction to obtain solid dry substance. 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 1 hour at the temperature of 400 ℃ to obtain the nitrogen-doped titanium dioxide nano catalyst material with high catalytic activity under visible light. In the activity test of the catalyst material, the apparent rate constant k of the first-order reaction kinetics of the catalyst for catalyzing and degrading phenol is 3.86 multiplied by 10-3min-1The first order kinetic apparent rate constant k is 1.04X 10 for titanium dioxide powder (P25, Degussa)-3min-13.7 times of that of the titanium dioxide, which is attributed to the fact that the nitrogen doping technology enables the photoresponse wavelength to be red-shifted to a visible light region, enhances the absorption of available light, inhibits the recombination of electrons and holes, prolongs the service life of the holes and further improves the photocatalytic activity of the titanium dioxide.
The ultraviolet-visible absorption spectra (UV-Vis) of the nitrogen-doped titanium dioxide nano catalyst material with high catalytic activity and the titanium dioxide powder (P25, Degussa) are shown in fig. 1, and the nitrogen-doped titanium dioxide nano catalyst material and the titanium dioxide powder (P25, Degussa) have almost equally strong absorption in the ultraviolet region; in the visible light region, the light absorption of the nitrogen-doped titanium dioxide nano-catalyst material is significantly higher than that of titanium dioxide powder (P25, Degussa). This is attributed to the fact that the nitrogen doping technique red-shifts the photoresponse wavelength into the visible region, enhancing the absorption of visible light.
Example 2
20ml of ammonia water solution (0.5M/L) and 20ml of titanium sulfate (the mass percentage content is more than 40.0%) are subjected to precipitation reaction 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 oven directly, treating at 120 deg.C for 4 hr, evaporating to remove water and part of alcohol substances generated in reaction to obtain solid dry substance. And grinding the solid dried substance to make the particles uniform and reduce soft agglomeration. Then placing the titanium dioxide nano catalyst material in a muffle furnace, and calcining the titanium dioxide nano catalyst material for 1 hour at the temperature of 400 ℃ to obtain the nitrogen-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 3.41 multiplied by 10-3min-1The first order kinetic apparent rate constant k is 1.04X 10 for titanium dioxide powder (P25, Degussa)-3min-13.3 times of the total weight of the powder.
Example 3
20ml of ammonia water (0.5M/L) and 20ml of tetrabutyl titanate (the mass percentage content is more than 98.0 percent) are subjected to precipitation reaction until white precipitate is completely generated. Heating the white precipitate in oven directly, treating at 120 deg.C for 4 hr, evaporating to remove water and part of alcohol substances generated in reaction to obtain solid dry substance. And grinding the obtained solid dried substance to ensure that the particles are uniform and soft agglomeration is reduced. Grinding, placing into a muffle furnace, calcining at 400 deg.C for 1 hr, 1.5 hr, and 2 hr to obtain visible lightThe nitrogen-doped titanium dioxide nano catalyst material with high catalytic activity. In a catalytic activity test, the apparent rate constants of first-order reaction kinetics of the catalyst material for catalyzing and degrading phenol are respectively 3.86-10-3min-1、3.81×10-3min-1、3.76×10-3min-1. It can be seen that after heat treatment for 1 hour, the nitrogen-doped titanium dioxide nano catalyst material with high catalytic activity under visible light is formed.
Example 4
In order to examine the influence of the kind of nitrogen dopant on the preparation of the nitrogen-doped titanium dioxide nano powder, ammonia gas and urea were tried in addition to ammonia water, and other experimental conditions such as the concentration of the nitrogen dopant and the experimental conditions were the same as those of example 3. In the test of catalytic activity of the synthesized nitrogen-doped titanium dioxide nano catalyst material, the apparent rate constants of the first-order reaction kinetics of the catalyst material for catalyzing and degrading phenol are respectively 3.57 multiplied by 10-3min-1、3.06×10-3min-1The first-order reaction kinetic apparent rate constant k is 1.04X 10 which is superior to that of titanium oxide powder (P25, Degussa)-3min-1。
Claims (9)
1. A method for preparing a nitrogen-doped titanium dioxide nano material with photocatalytic activity is characterized in that the method adopts a nitrogen doping technology to synthesize the nitrogen-doped modified titanium dioxide nano material, nitrogen elements are doped in crystal lattices of titanium dioxide crystals, and the nitrogen elements are doped in crystal gaps of the titanium dioxide crystals, wherein the weight percentage of 3 elements in the nitrogen-doped titanium dioxide nano material is as follows: the titanium accounts for 60.01to 60.20 percent, the oxygen accounts for 36.8 to 39.89 percent, and the nitrogen accounts for 0.10 to 3.00 percent.
2. The process for the preparation of photocatalytically active nitrogen-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 aqueous solution of nitrogen dopant, 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 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 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 nitrogen-doped titanium dioxide nano material.
3. The method for producing a photocatalytically active nitrogen-doped titanium dioxide nanomaterial according to claim 1 or 2, wherein the produced nitrogen-doped titanium dioxide nanomaterial is in an anatase form or coexists in an anatase form and a rutile form, and nitrogen is doped in both crystal lattices and crystal gaps of the titanium dioxide crystal material.
4. The method of claim 1 or 2, wherein the nitrogen-doped titanium dioxide nanomaterial has catalytic activity under both visible light and ultraviolet light, and the light source used is natural light, artificial simulated sunlight or ultraviolet light.
5. The method for preparing the photocatalytically active nitrogen-doped titanium dioxide nanomaterial according to claim 2, wherein the titanium precursor comprises titanium alkoxide and inorganic titanium salt, and the titanium alkoxide comprises one or a combination of two 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 preparing photocatalytically active nitrogen-doped titanium dioxide nanomaterial according to claim 2The method is characterized in that the nitrogen dopant is as follows: NH (NH)4OH，CO(NH2)2Ammonia gas (NH)3) And the like, ammonia derived substances and ammonium salts.
7. The method of claim 2, wherein the drying time of the white precipitate to the solid dried substance is 20 minutes or more and the drying temperature is 200 ℃ or less.
8. The method of claim 2 or 7, wherein the white precipitate is dried by direct heating or natural drying.
9. The method for preparing the photocatalytically active nitrogen-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 3-10 ℃/min.
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| CN100408185C (en) * | 2006-08-08 | 2008-08-06 | 南开大学 | Method for preparing nitrogen-doped nanometer titanium dioxide catalyst with high activity for visible light range |
| CN102275975A (en) * | 2011-06-01 | 2011-12-14 | 重庆工商大学 | Synthetic method for preparing nanometer cuprous oxide from nitrogen-doped cuprous oxide |
| CN102631908A (en) * | 2012-04-09 | 2012-08-15 | 北京理工大学 | N-doped nano-TiO2 and shock wave preparation method thereof |
| CN103894218A (en) * | 2014-04-09 | 2014-07-02 | 莆田学院 | Titanium dioxide mesoporous microsphere photocatalytic material co-doped with nitrogen and fluorine and preparation method of material |
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| CN100408185C (en) * | 2006-08-08 | 2008-08-06 | 南开大学 | Method for preparing nitrogen-doped nanometer titanium dioxide catalyst with high activity for visible light range |
| CN102275975A (en) * | 2011-06-01 | 2011-12-14 | 重庆工商大学 | Synthetic method for preparing nanometer cuprous oxide from nitrogen-doped cuprous oxide |
| CN102275975B (en) * | 2011-06-01 | 2013-03-13 | 重庆工商大学 | Synthetic method for preparing nanometer cuprous oxide from nitrogen-doped cuprous oxide |
| CN102631908A (en) * | 2012-04-09 | 2012-08-15 | 北京理工大学 | N-doped nano-TiO2 and shock wave preparation method thereof |
| CN103894218A (en) * | 2014-04-09 | 2014-07-02 | 莆田学院 | Titanium dioxide mesoporous microsphere photocatalytic material co-doped with nitrogen and fluorine and preparation method of material |
| CN103894218B (en) * | 2014-04-09 | 2016-03-23 | 莆田学院 | A kind of nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material and preparation method thereof |
| CN104248967A (en) * | 2014-06-17 | 2014-12-31 | 扬州大学 | Vapor phase method for preparation of porous carrier supported nitrogen doped titanium dioxide |
| CN104138766A (en) * | 2014-08-11 | 2014-11-12 | 中国建材国际工程集团有限公司 | Preparation method of N-doped TiO2 film capable of achieving visible light catalysis |
| CN110944749A (en) * | 2017-05-10 | 2020-03-31 | 卡罗比亚咨询有限责任公司 | Nano-functionalized scaffolds and methods of producing same |
| CN110944749B (en) * | 2017-05-10 | 2023-11-24 | 卡罗比亚咨询有限责任公司 | Nanometer functional bracket and production method thereof |
| CN107159295A (en) * | 2017-06-01 | 2017-09-15 | 苏州大学 | A kind of inverse opal materials derived of visible light photocatalytic degradation of organic pollutants and preparation method thereof |
| CN107159295B (en) * | 2017-06-01 | 2022-08-12 | 苏州大学 | Reverse protein stone material for visible light catalytic degradation of organic pollutants and preparation method thereof |
| CN107675326A (en) * | 2017-09-20 | 2018-02-09 | 苏州白云纺织科技发展有限公司 | A kind of preparation method of the ultra-thin shuttle-woven fabric of ultraviolet light catalytic antimicrobial water-proof function |
| CN107675326B (en) * | 2017-09-20 | 2020-12-15 | 苏州白云纺织科技发展有限公司 | Preparation method of ultra-thin tatted fabric with ultraviolet-resistant catalytic antibacterial waterproof function |
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