CN101204648A - Method for preparing photocatalyst doping with mesopore nanometer titanium oxide - Google Patents
Method for preparing photocatalyst doping with mesopore nanometer titanium oxide Download PDFInfo
- Publication number
- CN101204648A CN101204648A CNA200610134927XA CN200610134927A CN101204648A CN 101204648 A CN101204648 A CN 101204648A CN A200610134927X A CNA200610134927X A CN A200610134927XA CN 200610134927 A CN200610134927 A CN 200610134927A CN 101204648 A CN101204648 A CN 101204648A
- Authority
- CN
- China
- Prior art keywords
- titanium oxide
- solution
- mesoporous
- doped mesoporous
- doping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002019 doping agent Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 18
- 229910052740 iodine Inorganic materials 0.000 claims description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 17
- 239000011630 iodine Substances 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000010335 hydrothermal treatment Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- -1 isopropyl ester Chemical class 0.000 claims description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 4
- 229910052751 metal Inorganic materials 0.000 abstract 3
- 238000001338 self-assembly Methods 0.000 abstract 1
- 239000002159 nanocrystal Substances 0.000 description 20
- 229910052755 nonmetal Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910003087 TiOx Inorganic materials 0.000 description 7
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000004887 air purification Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a preparation technique of a doped photocatalyst of mesoporous nanocrystalline titanium oxide, in particular to a method of preparing non-metallic ion-doped photocatalyst of mesoporous nanocrystalline titanium oxide by two hydrothermal processes. By adopting the invention, mesoporous structured nanocrystalline titanium oxide doped with non-metallic elements can be acquired; a preparation method of doping (nitrogen-doping and iodine-doping) and effectively combing the non-metallic elements with mesoporous structure is adopted, which is characterized in that proper dopant is selected and two hydrothermal processes are carried out: seed crystal of titanium oxide is acquired in the first hydrothermal process and added with the dopant; seed crystal acquired in the first hydrothermal process is utilized. The mesoporous structure can be obtained through self assembly, and then the mesoporous structured nanocrystalline titanium oxide doped with non-metallic elements is acquired. The photocatalyst thus prepared has the advantages of a big-ratio superficial area, small grain size, and high visible absorption, etc., and as the mesoporous structure constructed by nanocrystalline particles has good auto-deposition effect, the invention can hopefully be applied in water processing.
Description
Technical field
The present invention relates to the technology of preparing of Doped Mesoporous nano titanium oxide photocatalyst, be specially and utilize two step water-heat processes to prepare the method for nonmetallic ion-doped mesopore nano titanium oxide photocatalyst, be expected to be used for efficient water treatment procedure.
Background technology
In light-catalyzed reaction process generation redox reaction, can effectively remove pollutant, therefore in air cleaning and water field of purification the unrivaled superiority of conventional process mode is arranged, such as advantage such as efficient, economic, workable, that cyclicity is good.
Because the nano-titanium oxide plurality of advantages (as efficient, environmental friendliness, nontoxic and cheap etc.), it is considered to be used for up to now the sky G﹠W and purifies the most promising photochemical catalyst.(3.2eV) is bigger because of the titanium oxide band gap, and can only bring into play its higher catalytic performance at ultraviolet region, but the content of sunshine middle-ultraviolet lamp has only about 4%, so this contradiction has limited the extensive use of nano-crystal titanium oxide photochemical catalyst greatly.Bring into play performance for nano-crystal titanium oxide is reached under 45% visible light even the indoor light at solar spectrum content, need carry out modification nano-crystal titanium oxide.
Nonmetal doping is proved to be a kind of effective modified method, mainly comprises the doping of C, N, S, B, I etc.Can effectively increase the absorption of visible light by nonmetal doping, make photochemical catalyst under visible light, also can bring into play its catalytic performance.And suitable pore-size distribution (having the aperture) at the 2-50nm central hole structure, not only have provide more reaction positions than bigger serface, and suitable fluid molecule diffusion admittance improves Pollutants Diffusion reaction interface speed, thereby promotes the carrying out of light-catalyzed reaction.
Yet the performance difference of the at present different photochemical catalysts that preparation process obtained is very big, and tracing it to its cause is because doping process and foreign atom are long-pending to titania surface, crystallite dimension, crystal formation and form the difference that defective etc. is caused.Existing simultaneously preparation method is difficult to nonmetal doping and the combination of formation central hole structure.
Obtain all to have the nano-crystal titanium oxide photochemical catalyst of high catalytic activity at ultraviolet and visible region, but just need a kind of controlled doping attitude, crystal formation, crystallite dimension, surface area etc. to influence the synthetic method of the key factor of catalytic performance, nonmetal doping and nano-crystal titanium oxide be can realize, highly effective air purification air and water treatmenting performance obtained having with central hole structure.
Summary of the invention
The invention provides a kind of method for preparing the Doped Mesoporous nano titanium oxide photocatalyst, solve the nano-titanium oxide that existing method is difficult to realize and have nonmetal doping and central hole structure simultaneously, solve problems such as the performance difference of photochemical catalyst is bigger simultaneously.
Technical scheme of the present invention is:
A kind of method for preparing the Doped Mesoporous photochemical catalyst comprises the steps:
1. the titaniferous presoma is dissolved in the organic solvent, the volume ratio between titaniferous presoma and the organic solvent is 1: (1-300) (preferred proportion is 1: 5-20), stir about 1h-10h (being preferably 3-5h) forms finely dispersed solution; Subsequently it is added drop-wise to the deionized water solution (pH=0.5-5) of acidifying, the volume ratio between the deionized water solution of titaniferous presoma and acidifying is 1: (1-300) (preferred proportion is 1: 5-20) stir about 1h-48h (being preferably 10h-20h); Formed homodisperse emulsion after the stirring, gained emulsion heat treated in reactor heats 1h-72h (being preferably 2h-12h) down 50 ℃-200 ℃ (being preferably 60 ℃-120 ℃); Adulterant can be chosen in before the heat treated or after the heat treatment and join in the reaction system, and the part by weight between adulterant and the titaniferous presoma is 1: (1-1000) (preferred proportion is 1: 50-200), stir after the adding.
The presoma of titaniferous is at least a kind of in metatitanic acid isopropyl ester, butyl titanate, the titanium tetrachloride etc.
Organic solvent is at least a kind of of ethylene glycol, ethanol, methyl alcohol, isopropyl alcohol, four butanols, ethyl acetate, butyl acetate etc.
Acidulant employed is at least a kind of in nitric acid, hydrochloric acid and the sulfuric acid, adds in the deionized water, and making pH value is 0.5-5, and the hydrolysis of titaniferous precursor can be effectively alleviated in the acidifying of deionized water.
Adulterant, nitrogen dopant are at least a kind of in thiocarbamide, urea, hexamethylenetetramine, sal-ammoniac, ammonium fluoride, ethylenediamine, triethylamine, the ammoniacal liquor etc.; The iodine adulterant is at least a kind of in iodine, lithium iodide, acid iodide, periodic acid, the KI etc.
2. the solution that step 1 is obtained is added drop-wise in the aqueous solution that is dissolved with surfactant in 20-100 ℃ of oil bath or water-bath, the concentration of aqueous surfactant solution is 1g/L-500g/L (being preferably 50g/L-200g/L), and solution that step 1 obtains and the volume ratio that is dissolved with between the aqueous solution of surfactant are 1: (0.1-100) (preferred proportion is 1: 0.2-10); Transfer in the reactor hydrothermal treatment consists 2h-72h (being preferably 8h-32h) under 60 ℃-200 ℃ (being preferably 80-150 ℃) after stirring 0.5h-24h (being preferably 5h-12h); With calcining 0.5h-24h (being preferably 1h-8h) down 200 ℃-700 ℃ (being preferably 300 ℃-550 ℃) after the reactants dry that is obtained, can obtain the Doped Mesoporous titanium oxide.
Surfactant has P123 (EO
20PO
70EO
20), F127 (EO
30PO
70EO
30), a kind of in the neopelex etc.
The present invention can obtain to have simultaneously nonmetal doping and central hole structure nano-crystal titanium oxide, employing can be simultaneously with nonmetal doping (nitrogen mixes, iodine mixes) and the effective preparation route that combines of central hole structure, be characterized in by selecting suitable dopants for use, by two step water-heat processes, water-heat process obtains the titanium oxide crystal seed and has added adulterant for the first time, water-heat process utilization for the second time process for the first time obtains doped seeds, obtain central hole structure, thereby finally obtain nonmetal doping, the nano-crystal titanium oxide of central hole structure (aperture is at 2-50nm).Prepared photochemical catalyst has bigger serface (scope 100-250m
2g
-1), little crystallite dimension (5nm-25nm), high visible absorption characteristics such as (400nm-700nm), the central hole structure powder that is made up by nano-crystalline granule has good auto-deposition effect simultaneously.
Advantage of the present invention is:
1. the present invention can realize mass preparation nonmetal doping mesopore nano-crystal titanium oxide, and the catalysis material that is obtained has bigger serface, little crystallite dimension, high-crystallinity, enriches characteristics such as pore structure and high visible absorption.Than general synthetic adulterated TiOx, this method preparation have a duct that the central hole structure nano-crystal titanium oxide can provide more active sites and reactant turnover, thereby have higher catalytic activity.The driving force that water-heat process provided simultaneously can promote effectively that foreign atom enters the titanium oxide lattice, thereby reaches more effective doping.
2. the prepared central hole structure of the present invention is built into by nano-crystalline granule, and bigger connectivity is arranged between the particle.With respect to general synthetic nano-crystalline granule, this structure helps separating from solution more, has solved the especially nano particle difficult problem that is difficult to separate from solution of powder granule to a great extent, has therefore increased its practicality.
3, but the inventive method is the synthetic method that controlled doping attitude, crystal formation, crystallite dimension, specific area etc. influence the key factor of catalytic performance, nonmetal doping and nano-crystal titanium oxide be can realize, highly effective air purification air and water treatmenting performance obtained having with central hole structure.
Description of drawings
Fig. 1 is a Doped Mesoporous photochemical catalyst transmission electron microscope photo.
Fig. 2 (A)-(B) mixes (A) for nitrogen and the XPS of iodine doping (B) mesopore photochemical catalyst characterizes.
The nitrogen adsorption curve of pore titanium oxide during Fig. 3 (A)-(B) mixes (A) for nitrogen and iodine mixes (B).
Fig. 4 (A)-(B) is the UV, visible light optical absorption spectra of Doped Mesoporous photochemical catalyst; (A) nitrogen mixes, and (B) iodine mixes.
Fig. 5 (A)-(D) is the performance curve of Doped Mesoporous photocatalyst for degrading dyestuff contaminant rhodamine B and methylene blue.
The specific embodiment
Below in conjunction with embodiment the present invention is illustrated:
Embodiment 1
The 10ml butyl titanate is dissolved in 35ml four butanols, forms finely dispersed solution behind the stirring 2h; Be added drop-wise to hydrolysis in the deionized water (pH=3) of 100ml nitric acid acidifying then, formed homodisperse emulsion after stirring 5h, gained emulsion is transferred to 100 ℃ of hydrothermal treatment consists 8h in the reactor of 250ml.Then the 1g hexamethylenetetramine is dissolved in the emulsion after the hydrothermal treatment consists, this drips of solution is added to the aqueous solution that 50ml is dissolved with 5g P123 surfactant.Whole dropping process drips 50 ℃ stirring in water bath, moves into again in the reactor behind the stirring 2h (evenly), behind 130 ℃ of following hydrothermal treatment consists 36h.Dry under 90 ℃ the emulsion that is obtained at last, (heating rate is 3 ℃ of min at 500 ℃ of following sintering 3h
-1, cooldown rate is 4 ℃ of min
-1), (sample is expressed as: NMT) to obtain nitrogen Doped Mesoporous nano-crystal titanium oxide.Fig. 1-(A) and (B) be the electromicroscopic photograph of made sample NMT, sample is by nanocrystalline form of granularity about 6nm as can be seen, and nanocrystalline aperture is about 9nm, and the aperture that is obtained is the accumulation hole of nano particle; The XPS high-resolution collection of illustrative plates of Fig. 2 (A) nitrogen element has confirmed that effective nitrogen mixes; Isothermal nitrogen adsorption shown in Fig. 3 (A) has shown the middle pore property of NMT, and specific area is 250m
2g
-1, illustration wherein obtains mesopore 2-50nm pore size distribution according to the BJH equation; By Fig. 4 (A) as can be seen titanium oxide at visible region higher light absorption has been arranged, visible absorption is＞420nm; Sample shows the degraded of dyestuff contaminant rhodamine B: no matter under ultraviolet light or under visible light, prepared nitrogen Doped Mesoporous titanium oxide NMT has the better degradation property than famous commodity titanium oxide P25, referring to Fig. 5 (A) and Fig. 5 (B), wherein no photocatalyst represents not add photochemical catalyst.Sample NMT Pyrogentisinic Acid's degradation rate sees Table 1.Leaving standstill nitrogen Doped Mesoporous titanium oxide NMT only needs 30min just to have the catalyst deposit more than 85% to get off, and P25 after leaving standstill 24h only less than under 20% the amount deposition.Obviously, prepared nitrogen Doped Mesoporous nano-crystal titanium oxide has the remarkable advantage of easier recovery.
Table 1. Doped Mesoporous photocatalyst for degrading phenol
In the table 1, UV light and visible light represent respectively under ultraviolet and visible light and shine.
The 16ml isopropyl titanate is dissolved in the 40ml isopropyl alcohol, forms finely dispersed solution behind the stirring 3h; Be added drop-wise to hydrolysis in the deionized water (pH=1) of nitric acid acidifying that 80ml is dissolved with 1g acid iodide and 0.1g iodine then, formed homodisperse emulsion after stirring 3h, gained emulsion is transferred to 70 ℃ of hydrothermal treatment consists 6h in the reactor of 250ml.Then 1g acid iodide and 0.1g iodine are dissolved in the emulsion after the hydrothermal treatment consists, this drips of solution is added to the aqueous solution that 70ml is dissolved with 6g P123 surfactant.Whole dropping process drips 50 ℃ stirring in water bath, stirs to move into again behind the 2h (evenly) in the reactor behind 150 ℃ of following hydrothermal treatment consists 48h.Dry under 90 ℃ the emulsion that is obtained at last, (heating rate is 3 ℃ of min at 400 ℃ of following sintering 3h
-1, cooldown rate is 4 ℃ of min
-1), (sample is expressed as: MTI) to obtain nitrogen Doped Mesoporous nano-crystal titanium oxide.Fig. 1-(C) and (D) be the electromicroscopic photograph of made sample MTI, sample is by nanocrystalline form of granularity about 8nm as can be seen, and nanocrystalline aperture is about 5nm, and the aperture that is obtained is the accumulation hole of nano particle; The XPS high-resolution collection of illustrative plates of Fig. 2 (B) I has confirmed that effective iodine mixes; Isothermal nitrogen adsorption shown in Fig. 3 (B) has shown the middle pore property of MTI, and specific area is 160m
2g
-1, illustration wherein obtains mesopore 2-50nm pore size distribution according to the BJH equation; By Fig. 4 (B) as can be seen titanium oxide at visible region higher light absorption has been arranged, visible absorption is＞420nm; Sample shows the degraded of dyestuff contaminant methylene blue: no matter under ultraviolet light or under visible light, prepared iodine Doped Mesoporous titanium oxide MTI has the better degradation property than famous commodity titanium oxide P25.Sample MTI Pyrogentisinic Acid's degradation rate sees Table 1.Leaving standstill iodine Doped Mesoporous titanium oxide MTI only needs 20min just to have the catalyst more than 90% to deposit from methylene blue solution, and P25 has only after leaving standstill 24h under 25% the amount deposition.Obviously, prepared iodine Doped Mesoporous nano-crystal titanium oxide has the remarkable advantage of easier recovery.
Embodiment 3
The 8ml titanium tetrachloride is dissolved in the 20ml ethylene glycol, forms finely dispersed solution behind the stirring 3h; Be added drop-wise to hydrolysis in the deionized water (pH=5) of 80ml hcl acidifying then, formed homodisperse emulsion after stirring 5h, gained emulsion is transferred to 120 ℃ of hydrothermal treatment consists 12h in the reactor of 250ml.Then 0.5g thiocarbamide and 0.8g hexamethylenetetramine are dissolved in the emulsion after the hydrothermal treatment consists, this drips of solution is added to the aqueous solution that 120ml is dissolved with 5g F123 surfactant.Whole dropping process drips 60 ℃ stirring in water bath, stirs to move into again behind the 2h (evenly) in the reactor behind 170 ℃ of following hydrothermal treatment consists 36h.Dry under 90 ℃ the emulsion that is obtained at last, (heating rate is 5 ℃ of min at 700 ℃ of following sintering 5h
-1, cooldown rate is 4 ℃ of min
-1), obtain nitrogen Doped Mesoporous nano-crystal titanium oxide.To obtain anatase type nitrogen Doped Mesoporous nano-crystal titanium oxide crystallite dimension be 8nm, nanocrystalline aperture is about 12nm, the aperture that is obtained is the accumulation hole of nano particle, specific area is 210m
2g
-1, visible absorption is＞420nm.Show that by degraded the nitrogen Doped Mesoporous nano-crystal titanium oxide that is obtained has in ultraviolet and visible region and represented high catalytic activity to serge blue, rhodamine B and phenol.
Comparative example 1
For further confirming the excellent properties of prepared nitrogen Doped Mesoporous nano-crystal titanium oxide, in the synthetic route of embodiment 1, prepared not Doped Mesoporous titanium oxide (MT) by not adding nitrogen dopant; Prepared nitrogen adulterated TiOx (NT) by not adding surfactant P123.From Fig. 5 (A), Fig. 5 (B) as can be seen, the degradation property of nitrogen Doped Mesoporous titanium oxide NMT all will be much better than the hollow titanium oxide MT that do not mix under ultraviolet still is visible light; The degradation rate of various catalyst Pyrogentisinic Acids shown in the table 1 NMT performance as can be seen is better than nitrogen adulterated TiOx NT equally.Therefore, nitrogen Doped Mesoporous titanium oxide no matter under ultraviolet (UV light) still under visible light (visible light) all have excellent catalytic performance.
Comparative example 2
For further confirming the excellent properties of prepared iodine Doped Mesoporous nano-crystal titanium oxide MTI, in the synthetic route of embodiment 2, prepared iodine adulterated TiOx (TI) by not adding surfactant P123.Degraded (seeing Table 1) to dyestuff contaminant methylene blue (seeing Fig. 5 (C), Fig. 5 (D)) and phenol shows, no matter iodine Doped Mesoporous nano-crystal titanium oxide MTI all has the superior catalytic performance than iodine adulterated TiOx TI under ultraviolet or under visible light.
Claims (4)
1. a method for preparing the Doped Mesoporous nano titanium oxide photocatalyst is characterized in that comprising the steps:
(1) the titaniferous presoma is dissolved in the organic solvent, the volume ratio between titaniferous presoma and the organic solvent is 1: (1-300), stir and form finely dispersed solution; Subsequently it is added drop-wise to the deionized water solution of acidifying, the deionized water solution pH=0.5-5 of acidifying, the volume ratio between the deionized water solution of titaniferous presoma and acidifying are 1: (1-300), stir; Formed homodisperse emulsion after the stirring, the heat treatment in reactor of gained emulsion is heated 1h-72h down at 50 ℃-200 ℃; Adulterant can be chosen in before the heat treatment or after the heat treatment and join in the reaction system, and middle part by weight is 1 between adulterant and the titaniferous presoma: (1-1000), adition process stirs;
The titaniferous presoma is at least a kind of in metatitanic acid isopropyl ester, butyl titanate, the titanium tetrachloride;
Organic solvent is at least a kind of in ethylene glycol, ethanol, methyl alcohol, isopropyl alcohol, four butanols, ethyl acetate, the butyl acetate;
Adulterant comprises nitrogen dopant or iodine adulterant, and nitrogen dopant is at least a kind of in thiocarbamide, urea, hexamethylenetetramine, sal-ammoniac, ammonium fluoride, ethylenediamine, triethylamine, the ammoniacal liquor; The iodine adulterant is at least a kind of in iodine, lithium iodide, acid iodide, periodic acid, the KI;
(2) solution that step 1 is obtained is added drop-wise in the aqueous solution that is dissolved with surfactant in 20-100 ℃ of oil bath or water-bath, the concentration of the solution surface activating agent aqueous solution is 1g/L-500g/L, and solution that step 1 obtains and the volume ratio that is dissolved with between the aqueous solution of surfactant are 1: (0.1-100); Transfer to after stirring in the reactor, at 60 ℃ of-200 ℃ of following heat treatment 2h-72h; With calcining 0.5h-24h down at 200 ℃-700 ℃ after the reactants dry that is obtained, can obtain the Doped Mesoporous titanium oxide.
2. according to the described method for preparing the Doped Mesoporous photochemical catalyst of claim 1, it is characterized in that: surfactant is a kind of in P123, F127, the neopelex.
3. according to the described method for preparing the Doped Mesoporous photochemical catalyst of claim 1, it is characterized in that: the deionized water solution acidulant employed of acidifying is at least a kind of in nitric acid, hydrochloric acid and the sulfuric acid.
4. according to the described method for preparing the Doped Mesoporous photochemical catalyst of claim 1, it is characterized in that: described heat treatment is hydrothermal treatment consists.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610134927XA CN101204648A (en) | 2006-12-20 | 2006-12-20 | Method for preparing photocatalyst doping with mesopore nanometer titanium oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610134927XA CN101204648A (en) | 2006-12-20 | 2006-12-20 | Method for preparing photocatalyst doping with mesopore nanometer titanium oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101204648A true CN101204648A (en) | 2008-06-25 |
Family
ID=39565267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200610134927XA Pending CN101204648A (en) | 2006-12-20 | 2006-12-20 | Method for preparing photocatalyst doping with mesopore nanometer titanium oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101204648A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760866A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN103007977A (en) * | 2012-12-25 | 2013-04-03 | 济南大学 | Preparation method of modified TiO2 with visible light response |
| CN105013461A (en) * | 2015-06-30 | 2015-11-04 | 宁波工程学院 | Application of N-doped TiO2 nano fiber in high-efficiency visible light photocatalyst |
| CN106145184A (en) * | 2016-06-21 | 2016-11-23 | 河南师范大学 | One has the high activity { TiO of 111} exposure high preferred orientation2the preparation method of microsphere |
| WO2018001176A1 (en) * | 2016-06-27 | 2018-01-04 | 中国科学院金属研究所 | Preparation method for controllable growth of heterogeneous seed mesoporous monocrystalline rutile titanium dioxide |
| CN108212187A (en) * | 2018-01-26 | 2018-06-29 | 湖北文理学院 | Fe adulterates Bi2O2CO3Preparation method and Fe the doping Bi of photochemical catalyst2O2CO3Photochemical catalyst |
| CN110395761A (en) * | 2019-07-26 | 2019-11-01 | 北京化工大学 | A kind of surface Co-doped ZnO composite material and preparation method and application |
| CN111871437A (en) * | 2020-06-14 | 2020-11-03 | 盐城师范学院 | Application method of carbon-nitrogen-doped indium oxide semiconductor photocatalytic material in preparation of hydrogen |
-
2006
- 2006-12-20 CN CNA200610134927XA patent/CN101204648A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760866A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN102760866B (en) * | 2011-04-26 | 2014-10-15 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN103007977A (en) * | 2012-12-25 | 2013-04-03 | 济南大学 | Preparation method of modified TiO2 with visible light response |
| CN103007977B (en) * | 2012-12-25 | 2014-10-29 | 济南大学 | Preparation method of modified TiO2 with visible light response |
| CN105013461A (en) * | 2015-06-30 | 2015-11-04 | 宁波工程学院 | Application of N-doped TiO2 nano fiber in high-efficiency visible light photocatalyst |
| CN106145184A (en) * | 2016-06-21 | 2016-11-23 | 河南师范大学 | One has the high activity { TiO of 111} exposure high preferred orientation2the preparation method of microsphere |
| WO2018001176A1 (en) * | 2016-06-27 | 2018-01-04 | 中国科学院金属研究所 | Preparation method for controllable growth of heterogeneous seed mesoporous monocrystalline rutile titanium dioxide |
| CN108212187A (en) * | 2018-01-26 | 2018-06-29 | 湖北文理学院 | Fe adulterates Bi2O2CO3Preparation method and Fe the doping Bi of photochemical catalyst2O2CO3Photochemical catalyst |
| CN110395761A (en) * | 2019-07-26 | 2019-11-01 | 北京化工大学 | A kind of surface Co-doped ZnO composite material and preparation method and application |
| CN110395761B (en) * | 2019-07-26 | 2020-09-04 | 北京化工大学 | Surface cobalt-doped zinc oxide composite material and preparation method and application thereof |
| CN111871437A (en) * | 2020-06-14 | 2020-11-03 | 盐城师范学院 | Application method of carbon-nitrogen-doped indium oxide semiconductor photocatalytic material in preparation of hydrogen |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101204648A (en) | Method for preparing photocatalyst doping with mesopore nanometer titanium oxide | |
| CN108940338B (en) | Potassium-doped porous carbon nitride photocatalyst and preparation method and application thereof | |
| Sun et al. | Mesocrystals for photocatalysis: a comprehensive review on synthesis engineering and functional modifications | |
| Cui et al. | Bi-based visible light-driven nano-photocatalyst: the design, synthesis, and its application in pollutant governance and energy development | |
| CN101927177B (en) | Preparation method of nitrogen-doped attapulgite load nano TiO2 visible light photocatalyst | |
| CN100998937B (en) | Fluorine doped-anatase type TiO2 collosol photo catalyst preparation method | |
| CN102335602B (en) | Bismuth tungstate composite photocatalyst, preparation method thereof, and application thereof | |
| CN100375650C (en) | Low temperature process of preparing carbon-doped mesoporous TiO2 visible light catalyst | |
| CN103894218B (en) | A kind of nitrogen, fluorin-doped titanium dioxide mesoporous microsphere catalysis material and preparation method thereof | |
| CN113289647B (en) | Biochar doped BiOBr x Cl 1-x Photocatalyst, preparation method and application | |
| CN101791548A (en) | Visible light catalyst BiVO4 and preparation method thereof | |
| CN102527423B (en) | Preparation method of molybdenum-nitrogen-codoped TiO2 granule and application thereof | |
| CN103349982B (en) | Bi2WO6 modified TiO2 nanobelt photocatalyst, preparation method and application thereof | |
| CN104971761A (en) | Nitrogen/sulfur-doped bismuth oxyhalide visible light catalysis material and preparation method thereof | |
| Ferreira et al. | Latest developments on TiO2-based photocatalysis: a special focus on selectivity and hollowness for enhanced photonic efficiency | |
| CN101444744A (en) | Zeolite-based nano bismuth molybdate visible light catalytic material and preparation method thereof | |
| CN102125831B (en) | Method for preparing mesoporous Bi2O3/TiO2 nano photocatalyst | |
| CN103480395A (en) | Preparation and application of core-shell-structure bismuth sulfide@bismuth oxide composite microspheres | |
| CN112958061A (en) | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof | |
| CN104096553B (en) | Titania solution based on Graphene composition and preparation method thereof | |
| CN103785131B (en) | A kind of method of catalyze and degrade organic pollutants | |
| CN104383909B (en) | A kind of controllable method for preparing of the pucherite particle/graphene complex of carbon cladding | |
| Fu et al. | Enhanced photocatalytic activity based on composite structure with downconversion material and graphene | |
| CN106799247A (en) | A kind of Bi24O31Br10/In2O3Heterojunction photocatalyst | |
| CN108212187B (en) | Fe doped Bi2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3Photocatalyst and process for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080625 |