CN100391595C - Method for preparing titanium oxide based photocatalysis material - Google Patents
Method for preparing titanium oxide based photocatalysis material Download PDFInfo
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- CN100391595C CN100391595C CNB200410009585XA CN200410009585A CN100391595C CN 100391595 C CN100391595 C CN 100391595C CN B200410009585X A CNB200410009585X A CN B200410009585XA CN 200410009585 A CN200410009585 A CN 200410009585A CN 100391595 C CN100391595 C CN 100391595C
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Abstract
The present invention belongs to the technical field of semiconductor photocatalysis materials, and particularly relates to a method for preparing photocatalysis material based on titanium dioxide. The present invention aims at improving the photocatalysis performance of materials in the process of preparing titanium dioxide. Two kinds of metal ions are simultaneously doped in the process of preparing titanium dioxide powder or thin films, so a novel photocatalysis material based on titanium dioxide is obtained. In addition, the material can effectively degrade most of pollutants in water body and air.
Description
Technical field
The invention belongs to the conductor photocatalysis material technical field, particularly the preparation method of titania based catalysis material.
Background technology
The conductor photocatalysis technology is that the semi-conducting material that utilizes ultraviolet light irradiation to have photocatalytic activity causes light-catalyzed reaction.TiO
2Catalysis material is a kind of conductor photocatalysis material that is subjected to extensive concern in recent years.Studies show that in a large number dyestuff, surfactant, organohalogen compounds, agricultural chemicals, oils, cyanide etc. can both be by TiO
2Finish photocatalytic degradation effectively, decolouring, detoxification, mineralising are the inorganic molecules material, thereby eliminate the pollution to environment.In addition, TiO
2That light-catalyzed reaction also has is nontoxic, catalytic activity is high, oxidability is strong, good stability, reaction condition gentleness, use that equipment needed thereby is simple, secondary pollution is little, easy operating, to low concentration pollutant and vapor phase contaminants also have good effect of removing, catalysis material to be easy to get, operating cost is low, to be expected with sunshine be to react advantage such as light source.Thereby, TiO
2Catalysis material is a kind of very promising material of curbing environmental pollution, and passes through TiO
2The work that the preparation of catalysis material and modification further improve its photocatalytic activity also just becomes the emphasis that people study.
In order to improve TiO
2Photocatalytic activity, it is material modified that the researcher adopts the method for metal ion mixing usually, and obtained certain effect.
Publication number is that the patent application of CN1350884A discloses a kind of titanium dioxide/silicon/molybdenum ternary composite Nano photochemical catalyst, makes by mix silica sol and titanium/molybdenum colloidal sol.
Publication number is that the patent application of CN1393290A discloses a kind of material for air purification and method for making and purposes, it is by add stabilizing agent in the titanium salt solution that is mixed with other slaine, add then that catalyst is hydrolyzed and the aging vitreosol that obtains, soak with carrier again and obtain.Contain multiple modified metal such as zinc, tin, tungsten, aluminium, strontium, indium, niobium, molybdenum, silicon, zirconium etc. in this scavenging material.
Although carry out the single metal-doped photocatalysis performance that can improve titanium dioxide to a certain extent, but still can not satisfy people it is dropped into requirement of actual application.Titanium dioxide is carried out the bimetallic ion doping, can obtain catalysis material than the powder better effects if of single metal ion mixing.
Summary of the invention
A purpose of the present invention is to improve material photocatalytic properties in the titanium dioxide preparation process, and this kind material can produce degradation to most pollutants in water body and the air effectively.
A further object of the present invention is to overcome uses the titania based catalysis material of single metal pair to carry out the defective that doping vario-property can not reach the good light catalytic effect, for example carry out iron, neodymium bimetallic ion doping, can make two metal ion species in titanium dioxide, produce the unexistent synergy of single metal, thus the titania based photocatalyst material that acquisition has good photocatalysis effect.
An also purpose of the present invention provides a kind of preparation method of titania based catalysis material.
The objective of the invention is to realize by the following technical solutions:
The preparation method of titania based catalysis material of the present invention is two metal ion species that mix simultaneously in preparation titanium dioxide powder or thin-film process, thereby obtains the catalysis material of photocatalysis better effects if.Its method may further comprise the steps:
(1) add hydrolysis inhibitor, titanium source, metal M 1 salting liquid, metal M 2 salting liquids in anhydrous organic solvent, vigorous stirring is about 30 minutes;
(2) under strong agitation, add entry in the solution that step (1) obtains, make water in the mixed solution: hydrolysis inhibitor: metal ions M 1: metal ions M 2: the mol ratio in titanium source is (1～100): (0.1～5): (0.001～0.10): (0.001～0.10): 1;
(3) with the colloidal sol ageing that obtains in the step (2) about 1 day, oven dry under 40～150 ℃ of situations about 2 days, 300～700 ℃ of following roastings about 1～24 hour; Obtain the titania based catalysis material that two metal ion species mix;
Described anhydrous organic solvent comprises absolute ethyl alcohol, acetone, cyclohexane or benzene etc.
Described hydrolysis inhibitor comprises red fuming nitric acid (RFNA), acetic acid or isopropyl alcohol etc.
The titanium source comprises butyl titanate or titanium tetrachloride etc. in the described step (1).
Described metal M 1 salting liquid is nitrate solution, sulfate liquor or the chloride solution of metal M 1 ion in this anhydrous organic solvent.
Described metal M 2 salting liquids are metal M 2 ions nitrate solution, sulfate liquor or chloride solutions in this anhydrous organic solvent.
The metal M 1 of described step (1) is selected from a kind of in Mg, Ca, Sr, Ba, Sc, Y, V, Cr, Mo, Mn, Fe, Co, Ni, the Zn element; Metal M 2 is selected from a kind of in the elements such as W, Ru, Sn, Pb, Cu, lanthanide series.
Oven dry in the described step (3) comprises heat oven dry and the oven dry of decompression heat.
Titania based catalysis material in the described step (3) comprises the particle of titanium dioxide, the film of titanium dioxide, and they all can load on other base material.
Titania based catalysis material of the present invention can make two metal ion species produce the unexistent synergy of single metal in titanium dioxide, thereby obtains to have the photocatalysis effect stronger than corresponding single metal ion mixing.This kind material can produce degradation to most pollutants in water body and the air effectively.
The specific embodiment
Embodiment 1, (the iron neodymium mixes and tests)
Preparation ferric nitrate ethanol solution 8g/L obtains solution B, and neodymium nitrate ethanol solution 4g/L obtains solution C, adds solution B 20ml, solution C 20ml in the 150ml absolute ethyl alcohol, red fuming nitric acid (RFNA) 5ml, butyl titanate 25ml, and vigorous stirring gets solution D; Under the vigorous stirring situation, in solution D, drip deionized water 35ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
Use to mix and not the powder of doped metal ion methylene blue is carried out photocatalytic degradation, be light source with the uviol lamp of two 20W, be catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, unadulterated TiO
2Powder is 30% 60 minutes photocatalytic degradation rate, only the corresponding degradation rate of the powder of doping iron ion is 36%, only the corresponding degradation rate of the powder of doping neodymium ion is 47%, the titania based catalysis material of iron, neodymium two metal ion species of having mixed is 69% 60 minutes photocatalytic degradation rate, has improved 130% than last doping.
Embodiment 2, (iron and the experiment of other metal ion mixing)
Preparation ferric sulfate absolute ethyl alcohol 0.03125mol/L solution obtains solution B, M2 ethanol solution 0.03125mol/L obtains solution C, in the 150ml absolute ethyl alcohol, add solution B 10ml, solution C 10ml, red fuming nitric acid (RFNA) 5ml, butyl titanate 25ml, vigorous stirring gets solution D; Under the vigorous stirring situation, in solution D, drip deionized water 35ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
Use to mix and not the powder of doped metal ion methylene blue is carried out photocatalytic degradation, be light source with the uviol lamp of two 20W, be catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, its reaction gained data such as table 1.
Table 1 iron and the experiment of other metal ion mixing
When TiO2 M1 M2 M1 doping M2 doping is not mixed only M1 mix only M2 doping codope
(mol) (mol) the assorted degradation rate degradation rate degradation rate of (mol) degradation rate
0.0625 Fe Ru 3.125×10
-4 3.125×10
-4 30.00％ 36％ 42.00％ 45.00％
0.0625 Fe Sn 3.125×10
-4 3.125×10
-4 30.00％ 36％ 33.00％ 39.00％
0.0625 Fe Pb 3.125×10
-4 3.125×10
-4 30.00％ 36％ 35.00％ 41.00％
0.0625 Fe Cu 3.125×10
-4 3.125×10
-4 30.00％ 36％ 38.00％ 42.00％
0.0625 Fe La 3.125×10
-4 3.125×10
-4 30.00％ 36％ 41.00％ 55.00％
0.0625 Fe Ce 3.125×10
-4 3.125×10
-4 30.00％ 36％ 37.00％ 48.00％
0.0625 Fe Lu 3.125×10
-4 3.125×10
-4 30.00％ 36％ 47.00％ 62.00％
0.0625 Fe Nd 3.125×10
-4 3.125×10
-4 30.00％ 36％ 47.00％ 69.00％
0.0625 Fe Sm 3.125×10
-4 3.125×10
-4 30.00％ 36％ 45.00％ 63.00％
0.0625 Fe Gd 3.125×10
-4 3.125×10
-4 30.00％ 36％ 55.00％ 71.00％
0.0625 Fe Hg 3.125×10
-4 3.125×10
-4 30.00％ 36％ 34.00％ 44.00％
Embodiment 3, (neodymium and the experiment of other metal ion mixing)
Preparation M1 ethanol solution 0.3125mol/L obtains solution B, neodymium nitrate ethanol solution 0.3125mol/L obtains solution C, adds 5ml red fuming nitric acid (RFNA), 25ml butyl titanate in the 150ml absolute ethyl alcohol, and B solution is some, C solution 1ml, vigorous stirring gets solution D; Under the vigorous stirring situation, in solution D, add deionized water 30ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
Use to mix and not the titanium dioxide powder of doped metal ion methylene blue is carried out photocatalytic degradation, be light source with the uviol lamp of two 20W, be catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, its reaction gained data such as table 2.
Table 2 neodymium and the experiment of other metal ion mixing
M1 did not fall M2 and falls codope and fall when TiO2 M1 M2 M1 doping M2 doping was mixed
(mol) (mol) (mol) degradation rate rate of separating rate of separating is separated rate
0.0625 Mg Nd 0.001875 7.5×10
-4 30％ 15％ 43％ 45％
0.0625 Ca Nd 0.001875 7.5×10
-4 30％ 22％ 43％ 46％
0.0625 Sr Nd 0.001875 7.5×10
-4 30％ 34％ 43％ 55％
0.0625 Ba Nd 0.001875 7.5×10
-4 30％ 14％ 43％ 46％
0.0625 Sc Nd 0.001875 7.5×10
-4 30％ 27％ 43％ 51％
0.0625 Y Nd 0.001875 7.5×10
-4 30％ 37％ 43％ 57％
0.0625 V Nd 0.001875 7.5×10
-4 30％ 41％ 43％ 65％
0.0625 Cr Nd 0.001875 7.5×10
-4 30％ 35％ 43％ 56％
0.0625 Mo Nd 0.001875 7.5×10
-4 30％ 35％ 43％ 58％
0.0625 Mn Nd 0.001875 7.5×10
-4 30％ 32％ 43％ 57％
0.0625 Fe Nd 0.001875 7.5×10
-4 30％ 33％ 43％ 67％
0.0625 Co Nd 0.001875 7.5×10
-4 30％ 28％ 43％ 56％
0.0625 Ni Nd 0.001875 7.5×10
-4 30％ 23％ 43％ 45％
0.0625 Zn Nd 0.001875 7.5×10
-4 30％ 31％ 43％ 47％
Embodiment 4, (experiment that concentration of iron changes)
Preparation iron chloride ethanol solution 0.0625mol/L obtains solution B, and neodymium nitrate ethanol solution 0.0625mol/L obtains solution C; Add 5ml red fuming nitric acid (RFNA), 25ml butyl titanate, some, the solution C 5ml of solution B in the 150ml absolute ethyl alcohol, vigorous stirring gets solution D; Under the vigorous stirring situation, in solution D, drip deionized water 30ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
Use to mix and not the titanium dioxide powder of doped metal ion methylene blue is carried out photocatalytic degradation, be light source with the uviol lamp of two 20W, be catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, its reaction gained data such as table 3.
The doping experiment that table 3 concentration of iron changes
M1 did not fall M2 and falls codope when TiO2 M1 M2 M1 doping M2 doping was mixed
(mol) (mol) (mol) degradation rate rate of separating is separated the rate degradation rate
0.0625 Fe Nd 1.25×10
-4 7.5×10
-4 30.00％ 31.00％ 43％ 43.00％
0.0625 Fe Nd 2.5×10
-4 7.5×10
-4 30.00％ 35.00％ 43％ 45.00％
0.0625 Fe Nd 3.75×10
-4 7.5×10
-4 30.00％ 41.00％ 43％ 48.00％
0.0625 Fe Nd 5.0×10
-4 7.5×10
-4 30.00％ 45.00％ 43％ 51.00％
0.0625 Fe Nd 6.25×10
-4 7.5×10
-4 30.00％ 46.00％ 43％ 57.00％
0.0625 Fe Nd 1.30×10
-3 7.5×10
-4 30.00％ 37.00％ 43％ 65.00％
0.0625 Fe Nd 1.875×10
-3 7.5×10
-4 30.00％ 33.00％ 43％ 67.00％
0.0625 Fe Nd 2.6×10
-3 7.5×10
-4 30.00％ 30.00％ 43％ 67.00％
0.0625 Fe Nd 3.125×10
-3 7.5×10
-4 30.00％ 26.00％ 43％ 62.00％
0.0625 Fe Nd 3.75×10
-3 7.5×10
-4 30.00％ 26.00％ 43％ 59.00％
0.0625 Fe Nd 4.375×10
-3 7.5×10
-4 30.00％ 23.00％ 43％ 56.00％
0.0625 Fe Nd 5.2×10
-3 7.5×10
-4 30.00％ 22.00％ 43％ 53.00％
0.0625 Fe Nd 5.625×10
-3 7.5×10
-4 30.00％ 18.00％ 43％ 48.00％
0.0625 Fe Nd 6.25×10
-3 7.5×10
-4 30.00％ 15.00％ 43％ 44.00％
Embodiment 5, (experiment that neodymium concentration changes)
Preparation ferric nitrate ethanol solution 0.03125mol/L obtains solution B, and neodymium chloride ethanol solution 0.03125mol/L obtains solution C; It is some to add 5ml red fuming nitric acid (RFNA), 25ml butyl titanate, solution B 10ml, solution C in the 150ml absolute ethyl alcohol, and vigorous stirring obtains solution D; Under the vigorous stirring situation, in solution D, add deionized water 30ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
The doping experiment that table 4 neodymium concentration changes
M1 degraded M2 degraded codope falls in TiO2 M1 M2 M1 doping ratio M2 doping ratio when not mixing
(mol) (mol) (mol) separates rate rate rate degradation rate
0.0625 Fe Nd 1.875×10
-3 6.25×10
-5 30.00％ 33％ 31％ 42％
0.0625 Fe Nd 1.875×10
-3 1.25×10
-4 30.00％ 33％ 32％ 47％
0.0625 Fe Nd 1.875×10
-3 2.50×10
-4 30.00％ 33％ 34％ 49％
0.0625 Fe Nd 1.875×10
-3 3.75×10
-4 30.00％ 33％ 35％ 53％
0.0625 Fe Nd 1.875×10
-3 5.00×10
-4 30.00％ 33％ 37％ 57％
0.0625 Fe Nd 1.875×10
-3 6.25×10
-4 30.00％ 33％ 41％ 60％
0.0625 Fe Nd 1.875×10
-3 7.50×10
-4 30.00％ 33.00％ 43％ 67.00％
0.0625 Fe Nd 1.875×10
-3 8.75×10
-4 30.00％ 33％ 48％ 72％
0.0625 Fe Nd 1.875×10
-3 1.00×10
-3 30.00％ 33％ 52％ 77％
0.0625 Fe Nd 1.875×10
-3 1.35×10
-3 30.00％ 33％ 57％ 73％
0.0625 Fe Nd 1.875×10
-3 2.70×10
-3 30.00％ 33％ 58％ 62％
0.0625 Fe Nd 1.875×10
-3 4.05×10
-3 30.00％ 33％ 47％ 53％
0.0625 Fe Nd 1.875×10
-3 5.40×10
-3 30.00％ 33％ 40％ 50％
0.0625 Fe Nd 1.875×10
-3 6.25×10
-3 30.00％ 33％ 32％ 41％
Embodiment 6, (changing the experiment of solution and hydrolysis inhibitor)
Use acetone to be the experiment of solvent, hydrolysis inhibitor as acetic acid.
The acetone soln 0.13mol/L of preparation M1 nitrate obtains solution B, and the acetone soln 0.13mol/L of M2 nitrate obtains solution C; Adding 5ml red fuming nitric acid (RFNA), 25ml butyl titanate, solution B 2.5ml, solution C 2.5ml, red fuming nitric acid (RFNA) 5ml vigorous stirring obtain solution D in 150ml acetone; Under the vigorous stirring situation, in solution D, drip deionized water 30ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
Use mixing and unadulterated powder carries out photocatalytic degradation to methylene blue, is light source with the uviol lamp of two 20W, is catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, unadulterated TiO
2Powder is 31% 60 minutes photocatalytic degradation rate, only the corresponding degradation rate of the powder of doping iron ion is 37%, only the corresponding degradation rate of the powder of doping neodymium ion is 49%, and the titania based catalysis material of two metal ion species that mixed is 71% 60 minutes photocatalytic degradation rate.
Use cyclohexane to be the experiment of solvent, hydrolysis inhibitor as acetic acid.
The cyclohexane solution 0.13mol/L of preparation M1 nitrate obtains solution B, and the cyclohexane solution 0.13mol/L of M2 nitrate obtains solution C; Adding 15ml acetic acid, 50ml butyl titanate, solution B 5ml, solution C 5ml, red fuming nitric acid (RFNA) 7ml vigorous stirring obtain solution D in the 150ml cyclohexane; Under the vigorous stirring situation, in solution D, drip deionized water 50ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 90 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
The titanium dioxide powder that use to mix and be not doped with metal ion carries out photocatalytic degradation to methylene blue, is light source with the uviol lamp of two 20W, is catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, unadulterated TiO
2Powder is 28% 60 minutes photocatalytic degradation rate, only the corresponding degradation rate of the powder of doping iron ion is 33%, only the corresponding degradation rate of the powder of doping neodymium ion is 42%, and the titania based catalysis material of two metal ion species that mixed is 56% 60 minutes photocatalytic degradation rate.
Use benzene to be the experiment of solvent, hydrolysis inhibitor as isopropyl alcohol.
The preparation ferric nitrate acetone soln 0.03125mol/L obtain solution B, lanthanum chloride acetone soln 0.03125mol/L obtain solution C; Adding 10ml isopropyl alcohol, 25ml butyl titanate, solution B 10ml, solution C 10ml, red fuming nitric acid (RFNA) 5ml vigorous stirring obtain solution D in 150ml benzene; Under the vigorous stirring situation, in solution D, drip deionized water 30ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
Use to mix and not the powder of doped metal ion methylene blue is carried out photocatalytic degradation, be light source with the uviol lamp of two 20W, be catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, unadulterated TiO
2Powder is 25% 60 minutes photocatalytic degradation rate, only the corresponding degradation rate of the powder of doping iron ion is 32%, the corresponding degradation rate of powder of lanthanum ion of only mixing is 43%, and the titania based catalysis material of two metal ion species that mixed is 55% 60 minutes photocatalytic degradation rate.
Embodiment 7, (changing the experiment of sintering temperature)
Preparation Fe (NO
3)
36H
2O ethanol solution 8g/L obtains solution B, Nd (NO
3)
36H
2O ethanol solution 4g/L obtains solution C; Adding 5ml red fuming nitric acid (RFNA), 25ml butyl titanate, solution B 20ml, solution C 20ml, red fuming nitric acid (RFNA) 5ml vigorous stirring obtain solution D in the 150ml absolute ethyl alcohol; Under the vigorous stirring situation, in solution D, drip deionized water 30ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F at corresponding down roasting some hrs, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
Utilize the photocatalysis experimental result such as the following table of the sample of different sintering temperatures and time.
Table 5 changes sintering temperature and the doping of time experiment
The sample that doping iron mixed simultaneously from the doping neodymium ion samples when sintering temperature sintering time did not mix
The degradation rate subsample
300 ℃ 2 hours 11.00% 10% 15% 21%
400 ℃ 2 hours 20.00% 24% 27% 35%
500 ℃ 2 hours 30.00% 36% 47% 69%
600 ℃ 2 hours 26.00% 31% 42% 52%
700 ℃ 2 hours 23.00% 26% 35% 45%
500 ℃ 1 hour 25.00% 27% 47% 53%
500 ℃ 4 hours 31.00% 38% 45% 68%
500 ℃ 8 hours 33.00% 35% 45% 62%
500 ℃ 12 hours 33.00% 34% 43% 57%
500 ℃ 16 hours 34.00% 33% 43% 56%
500 ℃ 20 hours 33.00% 36% 42% 52%
500 ℃ 24 hours 35.00% 38% 41% 50%
Embodiment 8, (changing the matrix experiment)
Preparation chromic nitrate ethanol solution 16g/L obtains solution B, and plumbi nitras ethanol solution 12g/L obtains solution C, adds solution B 10ml, solution C 10ml in the 150ml absolute ethyl alcohol, red fuming nitric acid (RFNA) 5ml, butyl titanate 30ml, and vigorous stirring gets solution D; Under the vigorous stirring situation, in solution D, drip deionized water 40ml, continue vigorous stirring 3 hours, obtain colloidal sol E; With czochralski method plated film on 5cm * 5cm titanium metal plate, 70 ℃ of oven dry, 500 ℃ of roastings 2 hours, the photocatalysis substrate behind the plated film of taking-up.
Use mixing and unadulterated substrate carries out photocatalytic degradation to methylene blue, is light source with the uviol lamp of a 20W, is catalyst material with the plated film meron, stirring reaction in the 1L beaker, unadulterated TiO
2Substrate is 15% 90 minutes photocatalytic degradation rate, only the corresponding degradation rate of the powder of chromium-doped ion is 19%, the corresponding degradation rate of powder of lead ion of only mixing is 24%, and the titania based catalysis material of two metal ion species that mixed is 42% 90 minutes photocatalytic degradation rate.
Embodiment 9 (changing the titanium source)
Preparation cobalt nitrate ethanol solution 8g/L obtains solution B, lutecium chloride ethanol solution 7g/L obtains solution C, in the 150ml absolute ethyl alcohol, add solution B 15ml, solution C 15ml, red fuming nitric acid (RFNA) 5ml, titanium tetrachloride 40ml, vigorous stirring gets solution D (keeping reaction system simultaneously under 10 ℃ of environment at the adding titanium tetrachloride); , under the vigorous stirring situation, in solution D, drip deionized water 35ml, continue vigorous stirring 3 hours, obtain colloidal sol E; Colloidal sol E 70 ℃ of oven dry 48 hours, is obtained powder F; With powder F 500 ℃ of following roastings 2 hours, the titania based catalysis material of two metal ion species that promptly obtain to have mixed.Do not add metal ion under the similarity condition, promptly obtain not have the titanium dioxide powder of doping.
Use to mix and not the powder of doped metal ion methylene blue is carried out photocatalytic degradation, be light source with the uviol lamp of two 20W, be catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, unadulterated TiO
2Powder is 60% 60 minutes photocatalytic degradation rate, only the corresponding degradation rate of the powder of doping iron ion is 70%, only the corresponding degradation rate of the powder of doping neodymium ion is 76%, and the titania based catalysis material of the iron that mixed, neodymium two metal ion species is 82% 60 minutes photocatalytic degradation rate.
Claims (5)
1. the preparation method of a titania based catalysis material is two metal ion species that mix simultaneously in preparation titanium dioxide powder process, and it is characterized in that: described method may further comprise the steps:
(1) in anhydrous organic solvent, adds hydrolysis inhibitor, titanium source, metal M 1 salting liquid, metal M 2 salting liquids, vigorous stirring;
(2) under strong agitation, in the solution that step (1) obtains, add entry, make water in the mixed solution: hydrolysis inhibitor: metal ions M 1: metal ions M 2: the mol ratio in titanium source is 1～100: 0.1～5: 0.001～0.10: 0.001～0.10: 1;
(3),,, obtain the titanium dioxide powder that two metal ion species mix 300～700 ℃ of following roastings 40～150 ℃ of oven dry down with the colloidal sol ageing that obtains in the step (2);
Described metal M 1 salting liquid is nitrate solution, sulfate liquor or the chloride solution of metal M 1 ion in this anhydrous organic solvent; Described metal M 1 is selected from a kind of in Mg, Ca, Sr, Ba, Sc, Y, V, Cr, Mo, Mn, Fe, Co, Ni, the Zn element, and the metal M in the sulfate liquor 1 does not comprise Ca, Sr, Ba, Sc, Y, V and Mo;
Described metal M 2 salting liquids are metal M 2 ions nitrate solution, sulfate liquor or chloride solutions in this anhydrous organic solvent; Described metal M 2 is selected from a kind of in W, Ru, Sn, Pb, Cu, the lanthanide series, and the metal M in the sulfate liquor 2 does not comprise W and Ru.
2. method according to claim 1 is characterized in that: described hydrolysis inhibitor is red fuming nitric acid (RFNA), acetic acid or isopropyl alcohol.
3. method according to claim 1 is characterized in that: the titanium source is butyl titanate or titanium tetrachloride in the described step (1).
4. method according to claim 1 is characterized in that: the oven dry in the described step (3) is the heat oven dry.
5. method according to claim 4 is characterized in that: described heat oven dry is the oven dry of decompression heat.
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| CN103101973B (en) * | 2013-01-16 | 2014-05-21 | 曲阜师范大学 | Vanadium and palladium-codoped nanometer titania gas-sensitive material as well as preparation method and applications thereof |
| CN104248955A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for preparing iron-doped rutile titanium dioxide |
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| CN105618103B (en) * | 2016-02-25 | 2018-05-11 | 济南大学 | A kind of preparation method of two-dimensional magnetic photochemical catalyst |
| CN105618104B (en) * | 2016-02-25 | 2019-04-02 | 济南大学 | A kind of preparation method of molybdenum oxide/titanium dioxide compound nanometer photocatalyst |
| CN106881094A (en) * | 2017-03-10 | 2017-06-23 | 北京科技大学 | A kind of Fe/Zn codopes TiO with visible light catalysis activity2Preparation method |
| CN110975860B (en) * | 2019-11-12 | 2022-12-23 | 河北地质大学 | Chromium-doped titanium-oxygen cluster nano catalytic material, preparation method and application |
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