CN102626650B - Preparation method of nanometer porous nitrogen doped titanium oxide visible photocatalyst - Google Patents
Preparation method of nanometer porous nitrogen doped titanium oxide visible photocatalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a nanometer porous nitrogen doped titanium oxide visible photocatalyst. The preparation method comprises the following steps: carrying out electrostatic self-assembly on titanium oxide nanosheets having negatively charged surfaces, and titanium oxide nanoparticles having positively charged surfaces to obtain a nanometer porous titanium oxide photocatalyst, and carrying out heat treatment nitridation to obtain the nanometer porous nitrogen doped titanium oxide visible photocatalyst. The method which allows titanium oxide crystal lattice oxygen to be partially substituted by nitrogen atoms to extend the absorption spectrum to a visible light region makes a visible light activity purpose be realized. The preparation method which has the advantages of simple preparation technology and equipment, easy operation, cheap and easily available required raw materials, short period of the preparation process, and high preparation efficiency is in favor of industrialized large-scale production. The nanometer porous nitrogen doped titanium oxide visible photocatalyst prepared through the preparation method of the invention has the advantages of high crystallization degree, high specific surface area, proper pore size distribution and the like, and has an obvious spectrum response in the visible light region.
Description
Technical field
The present invention relates to the preparation field of titanium oxide visible light catalyst, be specifically related to a kind of preparation method of nanoporous nitrogen-doped titanium dioxide photocatalyst.
Background technology
In today of urbanization and industrialization high speed development, the pollution problems such as water body, atmosphere have become countries in the world environmental issue urgently to be resolved hurrily.Environmental renovation is classified as cardinal task by national governments, and in succession drops into the research and development of huge fund for surrounding purifying material and environmental renovation technology.In recent years, Photocatalitic Technique of Semiconductor gets more and more people's extensive concerning aspect environmental pollution improvement, and demonstrates good application prospect.This technology is carried out at normal temperatures and pressures, and using reproducible light as the energy, thoroughly mineralising is decomposed the pollutant in air and water body, non-secondary pollution.In current surround lighting catalyticing research, titanium oxide (TiO
2) because of its abundant, cheap, fast light burn into chemically stable in source and to advantages such as human body nonhazardous, be regarded as optimal environment-friendly type catalysis material.
Block titanium oxide is because its specific area is low, thereby causes it to have the shortcomings such as poor to the capture ability of photon, light induced electron-hole is not easily separated, makes the overall catalytic efficiency of block titanium oxide lower.Titania meterial porous can be improved to the specific area of this material greatly, thereby improve its photocatalysis efficiency.About the preparation of ordered porous titania meterial, existing a lot of relevant report at home and abroad.Conventionally the synthetic method of porous titanium oxide mainly adopts cationic and nonionic surface active agent to synthesize as template, removes template and generally adopt the method for extraction and high-temperature roasting.But on the one hand, said method exists manufacturing cycle longer, the not high and duct of the products therefrom crystallinity shortcoming such as easily cave in; On the other hand, said method surfactant used is expensive, is unfavorable for large-scale production and application.Publication number is that the Chinese patent application of CN 101032684A discloses and a kind ofly adopts the method for preparing macroporous/mesoporous titanium dioxide catalyst without masterplate technology, but the specific area of resulting materials is low, pore volume is little, limited to the raising of photocatalytic activity.
Another major defect of titania meterial is that energy gap is larger, only ultraviolet light is had to activity, and at the shared energy of sunshine medium ultraviolet part that reaches ground less than 5%, and visible ray proportion is up to 45%, therefore, titania meterial is low to the overall utilization ratio of solar energy.Thereby the method that mainly adopts element doping is both at home and abroad carried out modification to it and is realized visible light-responded object.Publication number is the preparation method that the Chinese patent application of CN101347732A discloses a kind of poriferous titanium dioxide of transition metal iron ion doping, but the complex centre of the transition metal ions Chang Zuowei electron-hole of doping causes photocatalysis efficiency to reduce.In addition, the transition metal ions poor heat stability of doping, doping ion easily spins off from titanium oxide lattice with oxide form, has technical problem.Nonmetal nitrogen atom doping can effectively solve transient metal doped existing problem in the response of expansion titanium dioxide spectrum.Publication number is the preparation method that the Chinese patent application of CN 101066525A discloses a kind of micron level ordered porous aza titanium dioxide microballoon sphere, and prepared nitrogen dopant material has the visible light catalysis activity of obvious enhancing.But this preparation method, take nitrogen as nitrogenous source, must carry out nitrogenize in microwave plasma generation device, equipment needed thereby instrument is expensive, is unfavorable for large-scale promotion use.
Summary of the invention
The invention provides a kind of preparation method of nanoporous nitrogen adulterated TiOx visible light catalyst, by nitrogen-atoms part, replace the Lattice Oxygen in titanium oxide, expand its absorption spectrum to visible region, realize visible light-responded object, can improve the utilization rate of catalyst to solar energy.
The present invention is achieved by the following technical solutions:
A kind of preparation method of nanoporous nitrogen adulterated TiOx visible light catalyst, comprise: the TiOx nano particle of the TiOx nano sheet of surface band negative electrical charge and surface band positive charge is obtained to nanometer porous titanium oxide photochemical catalyst by electrostatic self-assembled, then obtain nanoporous nitrogen adulterated TiOx catalyst through heat treatment nitrogenize.
As preferably, the TiOx nano sheet of described surface band negative electrical charge is peeled off rear preparation with ethamine for peeling off reagent by the protonated titanate of stratiform.The reagent of peeling off using ethamine cheap and easy to get as the protonated titanate of stratiform, peels off into unimolecule lamellar structure by protonated stratiform titanate, prepares the suspension containing the TiOx nano sheet of the two-dimentional unimolecule lamellar structure of having of surface band negative electrical charge.Meanwhile, ethamine provides doping required nitrogen-atoms as nitrogenous source.
The protonated titanate of described stratiform can adopt prior art preparation.As preferably, the protonated titanate of described stratiform is H
0.7ti
1.825o
4h
2o, H
1.07ti
1.73o
4h
2o, HTi
1.75o
4h
2o or H
0.93ti
1.77o
4h
2o, all has the layer structure of lepidocrocite type.Have the layered titanate of lepidocrocite type, the metal oxide flaggy that its titanyl octahedral body forms has minimum charge density in numerous layered titanates, through organic amine or organic ammonium ionic interaction energe, effectively peels off layering to two-dimentional unimolecule lamellar structure.The method that the protonated titanate of stratiform can provide by people such as Sasaki prepares [Chem.Mater., 7 (1995) 1001-1007; Chem.Mater., 10 (1998) 4123-4128].The protonated titanate of stratiform is by the preparation of alkali metal stratiform titanate.The flaggy that the titanyl octahedral body that alkali metal stratiform titanate is 0.65nm～0.75nm by thickness forms and the alkali metal cation of interlayer form, wherein, and the flaggy surface band negative electrical charge of alkali metal stratiform titanate.The solid particle size of the alkali metal stratiform titanate of preparing by solid phase method is generally between 1 μ m～100 μ m.Alkali metal stratiform titanate is as typical cationic lamellar compound, the alkali metal cation of its interlayer has ion-exchange character, through its interlayer alkali metal cation of acid treatment, can be replaced and not change its layer structure and particle size by proton or proton hydrate, obtain the protonated titanate of stratiform.Interlayer proton or the proton hydrate of the protonated titanate of stratiform have acid activity, and acid-base reaction can occur.Add after ethamine, ethamine is combined with interlayer proton or the proton hydrate of the protonated titanate of stratiform, ethamine intercalation is to the interlayer of the protonated titanate of stratiform, after ultrasonic processing, flaggy separates, after layering, obtaining thickness is the TiOx nano sheet of 0.65nm～0.75nm unimolecule lamellar structure, and the TiOx nano sheet of this unimolecule lamellar structure is all consistent, all electronegative with the flaggy of alkali metal stratiform titanate and the flaggy charging property of the protonated titanate of stratiform.Because flaggy under ultrasonic processing ruptures, finally can obtain lateral dimension is 0.1 μ m～10 μ m, and thickness is the TiOx nano sheet that 0.65nm～0.75nm has the unimolecule lamellar structure of extreme Two-Dimensional Anisotropic character.
As preferably, the TiOx nano sheet of described surface band negative electrical charge is two-dimentional monolayer structure.The lateral dimension of this two dimension monolayer is generally 0.1 μ m～10 μ m, and this two dimension monolayer thickness, generally at 0.65nm～0.75nm, has extreme Two-Dimensional Anisotropic character.
As preferably, the TiOx nano particle of described surface band positive charge is by preparing using acetic acid as inhibitor and by tetrabutyl titanate hydrolysis, thus the TiOx nano particle of the good surface band positive charge of preparation granular size homogeneity.In the preparation of the TiOx nano particle of surface band positive charge, acetic acid is also for reaction provides acid condition as inhibitor time, and its ionization gained proton is easily adsorbed on TiOx nano particle surface and makes gained TiOx nano particle surface with positive charge.
As preferably, the mass ratio of the TiOx nano particle of described surface band positive charge and the TiOx nano sheet of surface band negative electrical charge is 0.5～10: 1.Under preferred mass ratio, be conducive to the TiOx nano sheet of surface band negative electrical charge and the TiOx nano particle of surface band positive charge is combined, thereby be conducive to carry out electrostatic self-assembled.Further preferably, the mass ratio of the TiOx nano particle of described surface band positive charge and the TiOx nano sheet of surface band negative electrical charge is 1～6.25: 1, makes negative electrical charge and positive charge have better matching relationship, is more conducive to electrostatic self-assembled.
As preferably, the condition of described heat treatment nitrogenize be using ethamine as nitrogenous source at 250 ℃～600 ℃ calcination processing 1～10 hour, through heat treatment nitrogenize, nitrogen-atoms part is replaced to the Lattice Oxygen in titanium oxide.Further preferably, the condition of described heat treatment nitrogenize be using ethamine as nitrogenous source at 300 ℃～350 ℃ calcination processing 2 hours.
The preparation method of described nanoporous nitrogen adulterated TiOx visible light catalyst, specifically comprises the following steps:
1) protonated stratiform titanate is dispersed in water, then adds ethylamine solution, ultrasonic processing obtains the suspension containing the TiOx nano sheet of surface band negative electrical charge;
2) under stirring condition, in acetic acid aqueous solution, drip butyl titanate, after dropwising, start reaction and in course of reaction, drip supplementing water, after reaction, obtain the solution containing the TiOx nano particle of surface band positive charge;
3) under stirring condition, by step 2) in the solution containing the TiOx nano particle of surface band positive charge be added drop-wise to step 1) in suspension containing the TiOx nano sheet of surface band negative electrical charge, after dropwising, continue reaction 4～8 hours, then after standing 4～8 hours, through being dried, obtain pressed powder;
4) by step 3) in pressed powder calcination processing 1～10 hour at 250 ℃～600 ℃, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
Step 1) in, protonated stratiform titanate is dispersed in water, the water yield is not had to special requirement, the TiOx nano sheet after protonated stratiform titanate can being peeled off disperses to determine the water yield as benchmark completely.
As preferably, in the protonated titanate of described stratiform and ethylamine solution, the mass ratio of ethamine is 1: 0.25～1; Ethamine amount is limited to preferred scope, is not only conducive to peeling off of the protonated titanate of stratiform, but also be conducive to step 4) in nitrogen doping, nitrogen-atoms part is replaced to the Lattice Oxygen in titanium oxide.
As preferably, the ultrasonic processing time is 1～10 hour, can promote ethamine that protonated stratiform titanate is peeled off completely, and further preferred, the ultrasonic processing time is 2～4 hours.
Step 2) in, as preferably, in described butyl titanate, acetic acid aqueous solution, in acetic acid, acetic acid aqueous solution, the mass ratio of water, supplementing water is 34: 38～46: 46～54: 80～120; Reaction 1～10h, is conducive to prepare that granular size homogeneity is good, size is at the TiOx nano particle of nano level surface band positive charge.
Step 3) in, in the solution of the described TiOx nano particle containing surface band positive charge, in the TiOx nano particle of surface band positive charge and the suspension of the TiOx nano sheet containing surface band negative electrical charge, the mass ratio of the TiOx nano sheet of surface band negative electrical charge is 0.5～10: 1, be conducive to the TiOx nano sheet of surface band negative electrical charge and the TiOx nano particle of surface band positive charge is combined, thereby be conducive to carry out electrostatic self-assembled.Further preferably, in the solution of the described TiOx nano particle containing surface band positive charge, in the TiOx nano particle of surface band positive charge and the suspension of the TiOx nano sheet containing surface band negative electrical charge, the mass ratio of the TiOx nano sheet of surface band negative electrical charge is 1～6.25: 1, make negative electrical charge and positive charge there is better matching relationship, be more conducive to electrostatic self-assembled.
Step 4) in, as preferably, by step 3) in pressed powder calcination processing 2 hours at 300 ℃～350 ℃, ethamine is as nitrogenous source, in step 1) in add, in step 4) in after calcination processing, nitrogen-atoms part is replaced to Lattice Oxygen in titanium oxide, thereby prepares nanoporous nitrogen adulterated TiOx visible light catalyst.
The performance characterization of the prepared nanoporous nitrogen adulterated TiOx photochemical catalyst of the present invention comprises: X-ray diffraction (XRD) collection of illustrative plates is measured product phase structure, adopt ultraviolet-uisible spectrophotometer to measure the uv-visible absorption spectra of product, adopt high resolution transmission electron microscopy (HRTEM) to observe its micrographs and structure, adopt nitrogen its specific area of determining adsorption and pore-size distribution.
Compared with prior art, tool of the present invention has the following advantages:
The preparation method of nanoporous nitrogen adulterated TiOx visible light catalyst of the present invention, adopt the TiOx nano sheet of surface band negative electrical charge and the TiOx nano particle of surface band positive charge by electrostatic self-assembled, to obtain the nanoporous nitrogen adulterated TiOx visible light catalytic agent material of high-specific surface area, porous, avoided using expensive surfactant, greatly reduced the cost of preparation.Preparation method of the present invention peels off reagent simultaneously as doping nitrogen source using cheap ethamine as the protonated titanate of stratiform, and preparation process is environmentally friendly.Preparation method preparation technology of the present invention and equipment are simple, easy operating, and needed raw material is cheap and easy to get, and the preparation process cycle is short, and preparation efficiency is high, is conducive to large-scale industrialization and produces.
Nanoporous nitrogen adulterated TiOx visible light catalyst prepared by preparation method of the present invention has the advantages such as degree of crystallinity is high, specific area is high, pore-size distribution is suitable, has obvious spectral response in visible region.This nanoporous nitrogen adulterated TiOx visible light catalyst has very strong adsorption capacity and visible light catalysis activity, can effectively utilize solar energy to solve the existing pollutions such as water body, atmosphere, is of very high actual application value and wide application prospect.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the nanoporous nitrogen adulterated TiOx photochemical catalyst prepared of embodiment 1 and embodiment 2, wherein abscissa is angle of diffraction 2 θ, ordinate is diffracted intensity, the photochemical catalyst of corresponding embodiment 1 gained of a in Fig. 1, the corresponding embodiment 2 gained photochemical catalysts of b in Fig. 1;
Fig. 2 is the uv-visible absorption spectra of the nanoporous nitrogen adulterated TiOx photochemical catalyst prepared of embodiment 1 and embodiment 2, wherein abscissa is wavelength, ordinate is absorbance, the photochemical catalyst of corresponding embodiment 1 gained of a in Fig. 1, the corresponding embodiment 2 gained photochemical catalysts of b in Fig. 1;
Fig. 3 is the transmission electron microscope photo of the nanoporous nitrogen adulterated TiOx photochemical catalyst prepared of embodiment 1, and wherein arrow indication is TiOx nano sheet, and footage number is 50nm;
Fig. 4 is isothermal curve and the pore size distribution figure of the nanoporous nitrogen adulterated TiOx photochemical catalyst prepared of embodiment 1, and wherein in Fig. 4, a is nitrogen adsorption/desorption isothermal curve figure, and its abscissa is relative pressure, and ordinate is adsorption volume; In Fig. 4, b is pore size distribution figure, and wherein abscissa is pore size distribution, and ordinate is pore volume;
Fig. 5 is nanoporous nitrogen adulterated TiOx photochemical catalyst prepared by embodiment 1 and embodiment 2, the time comparison diagram of Visible Light Induced Photocatalytic methyl orange under commodity P25 titanium oxide and catalyst-free, and wherein, abscissa is light application time, ordinate is degradation rate; The corresponding catalyst-free of a in Fig. 5, the corresponding P25 titanium oxide of b in Fig. 5, the photochemical catalyst of corresponding embodiment 1 gained of c in Fig. 5, the photochemical catalyst of corresponding embodiment 2 gained of d in Fig. 5.
The specific embodiment
Embodiment 1
One, the preparation of the protonated titanate of stratiform
1) 3.22g Anhydrous potassium carbonate (commercially available), 0.55g Carbon Dioxide lithium (commercially available), 7.68g titanium oxide (commercially available) mixed grinding were calcined 20 hours after 1 hour at 1000 ℃, obtained 10g alkali metal stratiform titanate K
0.8ti
1.73li
0.27o
4;
Flaggy and the positively charged potassium ion of interlayer of the surface band negative electrical charge that this alkali metal stratiform titanate consists of titanyl octahedral body form, and lithium ion occupies the position of part titanium atom in flaggy titanyl octahedral body;
2) take the above-mentioned alkali metal stratiform of 2.3g titanate K
0.8ti
1.73li
0.27o
4, impregnated in 200mL concentration is 1molL
-1aqueous hydrochloric acid solution magnetic agitation, within every 24 hours, change an aqueous hydrochloric acid solution, filtration washing after three days, obtains the protonated titanate H of 2g stratiform at 25 ℃ after dry
1.07ti
1.73o
4h
2o.
After acid treatment, the lithium ion in the potassium ion of interlayer and titanyl octahedral body flaggy is detached completely, and flaggy still keeps original structure, and proton and proton hydrate occupy interlayer with the shared electric charge of compensation negative electrical charge flaggy.
Preparation process and conclusion can be specifically with reference to [Chem.Mater., 10 (1998) 4123-4128].
Two, the preparation of nanoporous nitrogen adulterated TiOx visible light catalyst
1) by protonated 1g stratiform titanate H
1.07ti
1.73o
4h
2o is scattered in 100g deionized water, (quality of ethylamine solution is 0.68g to add the commercially available ethylamine solution of 1mL, the weight percentage of the ethamine in ethylamine solution is 70%), ultrasonic processing obtains the suspension of 100mL containing the TiOx nano sheet of surface band negative electrical charge for 2 hours, wherein, containing the quality of the TiOx nano sheet of surface band negative electrical charge in the suspension of the TiOx nano sheet of surface band negative electrical charge, be 0.88g;
2) the commercial ice acetic acid of 42g is mixed with the deionized water of 50g, obtain acetic acid aqueous solution, in acetic acid aqueous solution, drip 34g butyl titanate, after dropwising, start reaction and in course of reaction, dropwise add 100g deionized water, after stirring reaction 3 hours, obtain the solution of the TiOx nano particle containing surface band positive charge that 200mL is transparent, wherein, gained is 10g containing the quality of the TiOx nano particle of surface band positive charge in the solution of the TiOx nano particle of surface band positive charge;
3) under stirring condition, the solution containing the TiOx nano particle of surface band positive charge of 44mL gained is dropped to 100mL step 1 with the speed of 10mL per minute) in the suspension of gained containing the TiOx nano sheet of surface band negative electrical charge, after dropwising, continue stirring reaction 6 hours, standing 6 hours subsequently, be finally placed in the dry pressed powder that obtains of baking oven of 100 ℃;
4) by step 3) in pressed powder be placed in Muffle furnace and be warming up at 300 ℃ calcination processing 2 hours, obtain 3g nanoporous nitrogen adulterated TiOx visible light catalyst.
The nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment is obtained, by x-ray powder diffraction instrument, obtain X-ray diffraction (XRD) collection of illustrative plates, as shown in a in Fig. 1, result shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; By ultraviolet-uisible spectrophotometer, obtain uv-visible absorption spectra, as shown in a in Fig. 2, result shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo as shown in Figure 3, shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles; As shown in Figure 4, result shows in nitrogen absorption test, and the specific area of this nanoporous nitrogen adulterated TiOx visible light catalyst is up to 215m2g
-1, aperture is 5.5nm.
Embodiment 2
Other implementation steps, with embodiment 1, only change heat treatment temperature, and Muffle furnace ascending order is warming up to 350 ℃ of calcinings 2 hours, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment is obtained, by x-ray powder diffraction instrument, obtain X-ray diffraction (XRD) collection of illustrative plates, as shown in b in Fig. 1, result shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; By ultraviolet-uisible spectrophotometer, obtain uv-visible absorption spectra, as shown in b in Fig. 2, result shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Embodiment 3
Other implementation steps are with embodiment 1, only change the mass ratio of the TiOx nano particle of surface band positive charge and the TiOx nano sheet of surface band negative electrical charge, change the solution of the TiOx nano particle containing surface band positive charge adding into 22mL, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Embodiment 4
Other implementation steps, with embodiment 3, only change heat treatment temperature, and Muffle furnace ascending order is warming up to 350 ℃ of calcinings 2 hours, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Other implementation steps are with embodiment 1, only change the mass ratio of the TiOx nano particle of surface band positive charge and the TiOx nano sheet of surface band negative electrical charge, change the solution of the TiOx nano particle containing surface band positive charge adding into 66mL, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Embodiment 6
Other implementation steps, with embodiment 5, only change heat treatment temperature, and Muffle furnace ascending order is warming up to 350 ℃ of calcinings 2 hours, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Embodiment 7
Other implementation steps are with embodiment 1, only change the mass ratio of the TiOx nano particle of surface band positive charge and the TiOx nano sheet of surface band negative electrical charge, change the solution of the TiOx nano particle containing surface band positive charge adding into 88mL, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Embodiment 8
Other implementation steps, with embodiment 7, only change heat treatment temperature, and Muffle furnace ascending order is warming up to 350 ℃ of calcinings 2 hours, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Embodiment 9
Other implementation steps are with embodiment 1, only change the mass ratio of the TiOx nano particle of surface band positive charge and the TiOx nano sheet of surface band negative electrical charge, change the solution of the TiOx nano particle containing surface band positive charge adding into 110mL, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Other implementation steps, with embodiment 9, only change heat treatment temperature, and Muffle furnace ascending order is warming up to 350 ℃ of calcinings 2 hours, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Embodiment 11
Other implementation steps, with embodiment 1, only add the amount of ethylamine solution in the suspension preparation process of change containing the TiOx nano sheet of surface band negative electrical charge, change the ethylamine solution adding into 2mL, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Embodiment 12
Other implementation steps, with embodiment 11, only change heat treatment temperature, and Muffle furnace ascending order is warming up to 350 ℃ of calcinings 2 hours, obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
The XRD collection of illustrative plates of the nanoporous nitrogen adulterated TiOx visible light catalyst that the present embodiment obtains shows, this nanoporous nitrogen adulterated TiOx visible light catalyst consists of the Anatase of high-crystallinity; Uv-visible absorption spectra shows, this nanoporous nitrogen adulterated TiOx visible light catalyst has obvious spectral absorption in visible region; Transmission electron microscope photo shows that TiOx nano sheet is scattered in arbitrarily between Titanium particles.
Application examples 1 (with the visible light catalysis activity of Visible Light Induced Photocatalytic methyl orange detecting catalyst)
The catalytically active assessment system of gained nanoporous nitrogen adulterated TiOx photochemical catalyst of the present invention is as follows: all photocatalysis tests are all carried out in the vitreosil reactor of 200mL, and course of reaction is cooling with condensed water, maintains 10 ℃; Take Azo Dye-Methyl Orange as target degradation product, the concentration of methyl orange is 10mgL
-1; Magnetic agitation between the stage of reaction; It is all 0.05g that catalytic amount used is tested in all photocatalysis, and the amount of methyl orange aqueous solution is 100mL; Visible light source is the xenon lamp of 300W, has similar sunshine spectrum, is less than the ultraviolet band of 420nm to guarantee that incident light is as visible ray with the filter plate elimination wavelength of 420nm; Before each light-catalyzed reaction illumination, under darkroom, stir 40 minutes to guarantee absorption-desorption balance; Each reaction continues 60 minutes, and once, each sampling amount is 4mL in sampling in every 10 minutes; With supercentrifugal process, catalyst solid is separation with solution, the residual quantity of methyl orange ultraviolet-visible light analysis of spectrum, the characteristic absorption wavelength of methyl orange is 463nm.Catalyst is selected respectively embodiment 1, and porous nitrogen adulterated TiOx photochemical catalyst prepared by embodiment 2 and commercially available P25 titanium oxide (German degussa company) are tested, and catalyst-free are set in contrast, and concrete outcome as shown in Figure 5.
As shown in Figure 5, according to visible light catalytic result, show, the visible light photocatalysis active of obvious enhancing compared commercial commercially available P25 titanium oxide ultraviolet light active catalyst and has by porous nitrogen adulterated TiOx photochemical catalyst prepared by the present invention, this is owing to existing nitrogen-atoms part to replace the Lattice Oxygen in titanium oxide in gained porous nitrogen adulterated TiOx photochemical catalyst of the present invention, and porous nitrogen adulterated TiOx catalyst of the present invention is had due to response visible ray.In addition, porous nitrogen adulterated TiOx photochemical catalyst prepared by the present invention has high-specific surface area, also further promote catalyst material of the present invention to the catching and absorption to organic pollution of photon, finally made porous nitrogen adulterated TiOx visible light catalyst prepared by the present invention, under visible ray, organic pollution be had to high degrading activity.
Claims (6)
1. the preparation method of a nanoporous nitrogen adulterated TiOx visible light catalyst, it is characterized in that, comprise: the TiOx nano particle of the TiOx nano sheet of surface band negative electrical charge and surface band positive charge is obtained to nanometer porous titanium oxide photochemical catalyst by electrostatic self-assembled, through heat treatment nitrogenize, obtain nanoporous nitrogen adulterated TiOx catalyst again, specifically comprise the following steps:
1) protonated stratiform titanate is dispersed in water, then adds ethylamine solution, ultrasonic processing obtains the suspension containing the TiOx nano sheet of surface band negative electrical charge;
The protonated titanate of described stratiform is H
0.7ti
1.825o
4h
2o, H
1.07ti
1.73o
4h
2o, HTi
1.75o
4h
2o or H
0.93ti
1.77o
4h
2o;
2) under stirring condition, in acetic acid aqueous solution, drip butyl titanate, after dropwising, start reaction and in course of reaction, drip supplementing water, after reaction, obtain the solution containing the TiOx nano particle of surface band positive charge;
3) under stirring condition, by step 2) in the solution containing the TiOx nano particle of surface band positive charge be added drop-wise in step 1) in the suspension containing the TiOx nano sheet of surface band negative electrical charge, after dropwising, continue reaction 4～8 hours, then after standing 4～8 hours, through being dried, obtain pressed powder;
4) by the calcination processing 1～10 hour at 250 ℃～600 ℃ of the pressed powder in step 3), obtain nanoporous nitrogen adulterated TiOx visible light catalyst.
2. the preparation method of nanoporous nitrogen adulterated TiOx visible light catalyst according to claim 1, is characterized in that, the mass ratio of the TiOx nano particle of described surface band positive charge and the TiOx nano sheet of surface band negative electrical charge is 0.5～10:1.
3. the preparation method of nanoporous nitrogen adulterated TiOx visible light catalyst according to claim 2, is characterized in that, the mass ratio of the TiOx nano particle of described surface band positive charge and the TiOx nano sheet of surface band negative electrical charge is 1～6.25:1.
4. the preparation method of nanoporous nitrogen adulterated TiOx visible light catalyst according to claim 1, is characterized in that, the condition of described heat treatment nitrogenize be using ethamine as nitrogenous source at 250 ℃～600 ℃ calcination processing 1～10 hour.
5. the preparation method of nanoporous nitrogen adulterated TiOx visible light catalyst according to claim 4, is characterized in that, the condition of described heat treatment nitrogenize be using ethamine as nitrogenous source at 300 ℃～350 ℃ calcination processing 2 hours.
6. the preparation method of nanoporous nitrogen adulterated TiOx visible light catalyst according to claim 1, is characterized in that, in step 1), in the protonated titanate of described stratiform and ethylamine solution, the mass ratio of ethamine is 1:0.25～1; Ultrasonic processing 1～10 hour;
Step 2) in, in described butyl titanate, acetic acid aqueous solution, in acetic acid, acetic acid aqueous solution, the mass ratio of water, supplementing water is 34:38～46:46～54:80～120; React 1～10 hour.
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