CN107321378A - A kind of photochemical catalyst of wide spectrum response and preparation method thereof - Google Patents
A kind of photochemical catalyst of wide spectrum response and preparation method thereof Download PDFInfo
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- CN107321378A CN107321378A CN201710658538.5A CN201710658538A CN107321378A CN 107321378 A CN107321378 A CN 107321378A CN 201710658538 A CN201710658538 A CN 201710658538A CN 107321378 A CN107321378 A CN 107321378A
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- titanium dioxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 230000004044 response Effects 0.000 title claims abstract description 42
- 238000001228 spectrum Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 239
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 73
- 239000002086 nanomaterial Substances 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 42
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 40
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 40
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 39
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002071 nanotube Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 229910020341 Na2WO4.2H2O Inorganic materials 0.000 claims description 9
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000007743 anodising Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- 229910002551 Fe-Mn Inorganic materials 0.000 claims description 3
- 229910003077 Ti−O Inorganic materials 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000003595 spectral effect Effects 0.000 abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of preparation method of the photochemical catalyst of wide spectrum response, the photochemical catalyst of the wide spectrum response is the bismuth tungstate dioxide composite titanium nano particle or nanotube of nitrogen Fe2O3 doping, and the preparation method of the photochemical catalyst of the wide spectrum response is as follows：Prepare titanium dioxide nano material；Nitrogen Fe2O3 doping is carried out to titanium dioxide nano material；Prepare the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping.Coupled ion doping vario-property of the present invention and semiconductors coupling modification technology, the spectral response range of photochemical catalyst is expanded near infrared band from below 387nm ultraviolet portion, the response of nano titanium dioxide photocatalyst visible ray and near infrared light is realized, the catalytic activity of nanometer titanium dioxide carbon photochemical catalyst is enhanced.
Description
Technical field
Field is manufactured the present invention relates to photochemical catalyst, and in particular to a kind of photochemical catalyst of wide spectrum response and its preparation side
Method.
Background technology
With the quickening of process of industrialization, environment and energy problem are increasingly serious.Air pollution, water pollution are arrived greatly, it is small to arrive
Indoor decoration pollution, in-vehicle exposure etc. all threaten the health of human body.In the last few years, photocatalysis technology was quickly grown, and was used extensively
In the field such as air and Water warfare, sterilization.Its reaction condition is gentle, with low cost, and can be driving force using solar energy,
Non-secondary pollution simultaneously, is that a kind of can alleviate energy shortage and can effectively prevent and treat the method for environmental pollution again.
Nano titanium oxide is as a kind of most common photochemical catalyst, with stable, economic, green non-hazardous of property etc.
Advantage, is widely used in photocatalysis field.But it is due to that titanium dioxide energy gap reaches 3.2eV, only incident wavelength is less than
387nm ultraviolet photophase, the profit to sunshine only accounts for 3~5%；On the other hand, the light induced electron of titanium dioxide holds with hole
Easily compound, photo-quantum efficiency is not high.Therefore urged by expanding spectral response range to nano-titanium dioxide modified and improving
It is current study hotspot to change efficiency.
Chinese patent CN201310199995 discloses a kind of Visible light-sensitive semiconductor composite photocatalytic material and its system
Preparation Method, is compounded with titanium dioxide and tungsten, bismuth, the photoresponse scope of composite is expanded to visible ray.But this method is answered
The quantum efficiency of condensation material is not still high, and photoresponse scope is still not extensive enough.
The content of the invention
To solve the above problems, the invention provides photochemical catalyst of a kind of wide spectrum response and preparation method thereof, this hair
It is bright to greatly promote the catalytic performance of broad stopband width photochemical catalyst, realize nano titanium dioxide photocatalyst to visible ray and
The response of near infrared light.
To realize the technical purpose, the technical scheme is that：A kind of preparation of the photochemical catalyst of wide spectrum response
Method, the photochemical catalyst of the wide spectrum response is the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping, the wide light
The preparation method for composing the photochemical catalyst of response is as follows：
1st, titanium dioxide nano material is prepared；The titanium dioxide nano material is titania nanoparticles or titanium dioxide
Titanium nanotube；
2nd, nitrogen Fe2O3 doping is carried out to titanium dioxide nano material；
3rd, the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping is prepared.
Wherein, the step 1) in, it can prepare nano titanium oxide using vaporization condensation process, collosol and gel, hydro-thermal method and receive
Rice grain, or titania nanotube is prepared using hydro-thermal method, template, anodizing, crystal powder resolution method.But prepare
Titania nanoparticles or titania nanotube are not limited to these methods.
Wherein, with hydro-thermal legal system titania nanotube the step of, is as follows：
1.1), by TiO2Powder particle is dissolved in NaOH solution, and stirring is to being sufficiently mixed；
1.2), above-mentioned solution is inserted in autoclave, then 120~180 DEG C of constant temperature 48h of temperature naturally cool to
Room temperature；
1.3) sample after cooling, is inserted into centrifuge separation, deionized water is then added to pH value weakly acidic pH；
1.4) hydrochloric acid solution cleaning sample, is used, then with deionized water cleaning sample to pH value weakly acidic pH；
1.5), separated using centrifuge, titania nanotube is obtained after drying.
It is preferred that, step 1.1) in NaOH solution concentration be 5~15mol/L.
It is preferred that, step 1.1) in TiO2Mass fraction in NaOH solution is 5~9%wt.
It is preferred that, step 1.2) in the autoclave that uses be the autoclave containing polytetrafluoroethyllining lining.
It is preferred that, step 1.4) in hydrochloric acid solution concentration be 0.1mol/L.
It is preferred that, step 1.5) in drying temperature be 60~100 DEG C.
Wherein, the step 2) method that titanium dioxide nano material carries out nitrogen Fe2O3 doping is had steps of：
2.1), by step 1) titanium dioxide nano material for preparing inserts in iron nitrate solution, soaks；
2.2) above-mentioned material, is inserted into tube furnace, ammonia atmosphere is maintained, heating obtains the titanium dioxide of Fe-Mn cycle and transference
Nano material.
It is preferred that, the step 2.1) in iron nitrate solution concentration be 0.05~0.2mol/L.
It is preferred that, the step 2.1) in soak time be 24h.
It is preferred that, the step 2.2) in heating temperature be 400~500 DEG C, heat 2~3h.
Wherein, the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping is prepared using hydro-thermal method.
It is preferred that, the step of preparing the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping is as follows：
3.1), by Bi (NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution respectively, and stirring is to being sufficiently mixed；
3.2), above-mentioned solution is moved into hydrothermal reaction kettle, and is put into step 2 wherein) titanium dioxide for preparing receives
Rice material, reaction naturally cools to room temperature after terminating；
3.3), obtained product deionized water and absolute ethyl alcohol are alternately rinsed, is then placed in drying box and dries, i.e.,
The bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping can be made.
It is preferred that, step 3.1) in Bi (NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution, quality point respectively
Number is respectively 0.5~1%wt and 0.2~0.4%wt.
It is preferred that, step 3.2) in 10~20h of hydro-thermal reaction, 120~200 DEG C of temperature.
It is preferred that, step 3.2) in hydrothermal reaction kettle be the hydrothermal reaction kettle containing teflon lined.
It is preferred that, step 3.3) in sample deionized water and absolute ethyl alcohol are alternately rinsed 5~8 times.
It is preferred that, step 3.3) in drying condition be 50~90 DEG C of dry 12h in drying box.
The present invention also provides a kind of photochemical catalyst of wide spectrum response, and the photochemical catalyst of the wide spectrum response is that nitrogen iron is mixed
Miscellaneous bismuth tungstate composite titanium dioxide nano material.
The bismuth tungstate composite titanium dioxide nano material of the nitrogen Fe2O3 doping has following structure：Fe is in ferric form
Replace part tetravalence Ti4+It is present in TiO2In lattice, N substitution O insertions TiO2Lattice, forms N-Ti-O networks.Titanium dioxide
Titanium exists in Anatase form, and bismuth tungstate exists with rhombic system, and bismuth tungstate is dispersed on the titanium dioxide, and both form
Heterojunction structure.
In the bismuth tungstate composite titanium dioxide nano material of the nitrogen Fe2O3 doping, wolframic acid bi content is 15~25%.It is preferred that
, wolframic acid bi content is 20%.
Preparation method of the present invention is specially：
1st, titanium dioxide nano material is prepared；The titanium dioxide nano material is titania nanoparticles or titanium dioxide
Titanium nanotube；Nanometer titanium dioxide titanium nano particle can be prepared, or uses hydro-thermal using vaporization condensation process, collosol and gel, hydro-thermal method
Method, template, anodizing, crystal powder resolution method prepare titania nanotube；
2nd, nitrogen Fe2O3 doping is carried out to titanium dioxide nano material
2.1st, the titanium dioxide nano material that step 1 is prepared is inserted into the ferric nitrate that concentration is 0.05~0.2mol/L
In solution, 24h is soaked；
2.2nd, above-mentioned material is inserted into tube furnace, maintains ammonia atmosphere, 400~500 DEG C of temperature heats 2~3h, obtains nitrogen
The titanium dioxide nano material of iron codope；
3rd, the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping is prepared
3.1st, by Bi (NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution respectively, and mass fraction is respectively
0.5~1%wt and 0.2~0.4%wt, stirring is to being sufficiently mixed；
3.2nd, above-mentioned solution is moved into the hydrothermal reaction kettle containing teflon lined, and is put into step 2 wherein and made
The titanium dioxide nano material got ready, reaction naturally cools to room temperature after terminating；
3.3rd, sample deionized water and absolute ethyl alcohol are alternately rinsed 5~8 times, be then placed in 50 in drying box~
90 DEG C of dry 12h, you can the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping is made.
Preparing titanium dioxide nano material can use but be not limited to following methods；The titanium dioxide nano material is two
Titanium dioxide nanoparticle or titania nanotube；Nanometer titanium dioxide can be prepared using vaporization condensation process, collosol and gel, hydro-thermal method
Titanium nano particle, or titania nanotube is prepared using hydro-thermal method, template, anodizing, crystal powder resolution method.With
Hydro-thermal method is prepared exemplified by titania nanotube：
1.1st, by TiO2Powder particle is dissolved in NaOH solution, and stirring is to being sufficiently mixed；The concentration of NaOH solution be 5~
15mol/L；TiO2Mass fraction in NaOH solution is 5~9%wt；
1.2nd, above-mentioned solution is inserted in the autoclave containing polytetrafluoroethyllining lining, 120~180 DEG C of constant temperature of temperature
48h, then naturally cools to room temperature；
1.3rd, the sample after cooling is inserted into centrifuge separation, then adds deionized water to pH value weakly acidic pH；
1.4th, the hydrochloric acid solution cleaning sample for being 0.1mol/L with concentration, then with deionized water cleaning sample to pH value it is near in
Property；
1.5th, separated using centrifuge, titania nanotube is obtained after 60~100 DEG C of dryings.
The present invention is by TiO2Doped energy-band can be produced by carrying out ion doping, make TiO2Energy gap narrow, to spectrum ring
Answer scope to expand, the ion adulterated in addition can produce capture trap, increase the life-span of photo-generated carrier, strengthen catalytic performance.
Present invention incorporates the method for ion doping and semiconductors coupling, catalytic efficiency is on the one hand improved, on the other hand will
Spectral response range expands near infrared band from below 387nm ultraviolet portion.
The present invention uses the semiconductor and TiO of low energy gap width2It is combined, broad stopband width photocatalysis can be greatly promoted
The catalytic performance of agent, the semiconductor for being on the one hand combined wide-spectrum absorption has widened TiO2Spectral response range, on the other hand can be formed
Heterojunction structure induces electron-hole and reaches permanently effective separation.
The invention provides a kind of nano-TiO2The method of modifying of photochemical catalyst：Ion doping Fe and N is first passed through by spectrum
Response range extends to visible region, then further with semi-conducting material bismuth tungstate (Bi2WO6) compound, by spectral response model
Enclose and extend near infrared band, so as to lift the catalytic activity of photochemical catalyst, extend its application field.
Coupled ion doping vario-property of the present invention and semiconductors coupling modification technology, realize nano titanium dioxide photocatalyst
Response to visible ray and near infrared light, spectral response range expands near infrared band from below 387nm ultraviolet portion, increases
The strong catalytic activity of nanometer titanium dioxide carbon photochemical catalyst.
Brief description of the drawings
Fig. 1 is the photochemical catalyst of the preparation of embodiment 1 in the ultraviolet abosrption spectrogram to visible-range.
Fig. 2 is abosrption spectrogram of the photochemical catalyst in visible ray near infrared range of the preparation of embodiment 1.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below.Obviously, described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
A kind of preparation method of the photochemical catalyst of wide spectrum response, the photochemical catalyst of the wide spectrum response is nitrogen Fe2O3 doping
Bismuth tungstate composite titanium dioxide nano material, the preparation method of the photochemical catalyst of wide spectrum response is as follows：
1st, titanium dioxide nano material is prepared；The titanium dioxide nano material is titania nanoparticles or titanium dioxide
Titanium nanotube；
2nd, nitrogen Fe2O3 doping is carried out to titanium dioxide nano material；
3rd, the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping is prepared.
Wherein, the step 1) in, it can prepare nano titanium oxide using vaporization condensation process, collosol and gel, hydro-thermal method and receive
Rice grain, or titania nanotube is prepared using hydro-thermal method, template, anodizing, crystal powder resolution method.But prepare
Titania nanoparticles or titania nanotube are not limited to these methods.
Wherein, with hydro-thermal legal system titania nanotube the step of, is as follows：
1.1), by TiO2Powder particle is dissolved in NaOH solution, and stirring is to being sufficiently mixed；
1.2), above-mentioned solution is inserted in autoclave, then 120~180 DEG C of constant temperature 48h of temperature naturally cool to
Room temperature；
1.3) sample after cooling, is inserted into centrifuge separation, deionized water is then added to pH value weakly acidic pH；
1.4) hydrochloric acid solution cleaning sample, is used, then with deionized water cleaning sample to pH value weakly acidic pH；
1.5), separated using centrifuge, titania nanotube is obtained after drying.
It is preferred that, step 1.1) in NaOH solution concentration be 5~15mol/L.
It is preferred that, step 1.1) in TiO2Mass fraction in NaOH solution is 5~9%wt.
It is preferred that, step 1.2) in the autoclave that uses be the autoclave containing polytetrafluoroethyllining lining.
It is preferred that, step 1.4) in hydrochloric acid solution concentration be 0.1mol/L.
It is preferred that, step 1.5) in drying temperature be 60~100 DEG C.
Wherein, the step 2) method that titanium dioxide nano material carries out nitrogen Fe2O3 doping is had steps of：
2.1), by step 1) titanium dioxide nano material for preparing inserts in iron nitrate solution, soaks；
2.2) above-mentioned material, is inserted into tube furnace, ammonia atmosphere is maintained, heating obtains the titanium dioxide of Fe-Mn cycle and transference
Nano material.
It is preferred that, the step 2.1) in iron nitrate solution concentration be 0.05~0.2mol/L.
It is preferred that, the step 2.1) in soak time be 24h.
It is preferred that, the step 2.2) in heating temperature be 400~500 DEG C, heat 2~3h.
Wherein, the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping is prepared using hydro-thermal method.
It is preferred that, the step of preparing the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping is as follows：
3.1), by Bi (NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution respectively, and stirring is to being sufficiently mixed；
3.2), above-mentioned solution is moved into hydrothermal reaction kettle, and is put into step 2 wherein) titanium dioxide for preparing receives
Rice material, reaction naturally cools to room temperature after terminating；
3.3), obtained product deionized water and absolute ethyl alcohol are alternately rinsed, is then placed in drying box and dries, i.e.,
The bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping can be made.
It is preferred that, step 3.1) in Bi (NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution, quality point respectively
Number is respectively 0.5~1%wt and 0.2~0.4%wt.
It is preferred that, step 3.2) in 10~20h of hydro-thermal reaction, 120~200 DEG C of temperature.
It is preferred that, step 3.2) in hydrothermal reaction kettle be the hydrothermal reaction kettle containing teflon lined.
It is preferred that, step 3.3) in sample deionized water and absolute ethyl alcohol are alternately rinsed 5~8 times.
It is preferred that, step 3.3) in drying condition be 50~90 DEG C of dry 12h in drying box.
The photochemical catalyst of wide spectrum response prepared by the inventive method is that the bismuth tungstate composite titanium dioxide of nitrogen Fe2O3 doping is received
Rice material.
The bismuth tungstate composite titanium dioxide nano material of the nitrogen Fe2O3 doping has following structure：Fe is in ferric form
Replace part tetravalence Ti4+There is TiO2In lattice, N substitution O insertions TiO2Lattice, forms N-Ti-O networks.Titanium dioxide
Exist in Anatase form, bismuth tungstate exists with rhombic system, and bismuth tungstate is dispersed on the titanium dioxide, and both form different
Matter junction structure.
In the bismuth tungstate composite titanium dioxide nano material of the nitrogen Fe2O3 doping, wolframic acid bi content is 15~25%.
It is preferred that, wolframic acid bi content is 20%.
Embodiment 1
A kind of photochemical catalyst of wide spectrum response, is prepared using the following method：
1st, titania nanotube is prepared
1.1st, by TiO2Powder particle is dissolved in 10mol/L NaOH solution, and stirring is to being sufficiently mixed；TiO2In NaOH
Mass fraction in solution is 7%wt；
1.2nd, above-mentioned solution is inserted in the autoclave containing polytetrafluoroethyllining lining, 160 DEG C of constant temperature 48h of temperature, so
After naturally cool to room temperature；
1.3rd, the sample after cooling is inserted into centrifuge separation, then adds deionized water to pH value weakly acidic pH；
1.4th, the hydrochloric acid solution cleaning sample for being 0.1mol/L with concentration, then with deionized water cleaning sample to pH value it is near in
Property；
1.5th, separated using centrifuge, titania nanotube is obtained after 80 DEG C of dryings；
2nd, nitrogen Fe2O3 doping is carried out to titania nanotube
2.1st, the titania nanotube that step 1 is prepared is inserted in the iron nitrate solution that concentration is 0.1mol/L,
Soak 24h；
2.2nd, above-mentioned sample is inserted into tube furnace, maintains ammonia atmosphere, 450 DEG C of temperature heats 2h, obtains iron, nitrogen and is co-doped with
Miscellaneous titania nanotube；
3rd, bismuth tungstate titanium dioxide nanotube is prepared
3.1st, by Bi (NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution respectively, and mass fraction is respectively
1%wt and 0.3%wt, stirring is to being sufficiently mixed；
3.2nd, above-mentioned solution is moved into the hydrothermal reaction kettle containing teflon lined, and is put into step 2 wherein and made
The titania nanotube got ready, reaction naturally cools to room temperature after terminating；
3.3rd, sample deionized water and absolute ethyl alcohol are alternately rinsed 8 times, is then placed in drying box 90 DEG C and does
Dry 12h, you can the bismuth tungstate titanium dioxide nanotube of nitrogen Fe2O3 doping is made.
The product that the present embodiment is prepared, does material phase analysis by XRD and EDS and confirms as target product nitrogen Fe2O3 doping
Bismuth tungstate titanium dioxide nanotube.Its absorption spectrum is shown in Fig. 1 and Fig. 2 respectively.It can be seen from figure 1 that the present invention is relative to dioxy
Change titanium and the titanium dioxide (being respectively individually to be combined bismuth tungstate and independent nitrating, iron) of single ion doping, ultraviolet to visible
Optical range has higher absorbability and absorption efficiency.As it is clear from fig. 2 that the present invention is answered relative to titanium dioxide and single semiconductor
Close, there is higher absorbability and absorption efficiency in visible ray near infrared range.
From absorption spectrum, on the one hand photochemical catalyst prepared by the present invention produces the absorption of near-infrared, realizes wide spectrum optical
Catalysis, also as generation coupled mode hetero-junctions makes electronics be in respectively in different semiconductors from hole and realize carrier
Efficiently separate, increase photocatalysis efficiency.
Embodiment 2
1st, titania nanotube is prepared
1.1st, by TiO2Powder particle is dissolved in 15mol/L NaOH solution, and stirring is to being sufficiently mixed；TiO2In NaOH
Mass fraction in solution is 5%wt；
1.2nd, above-mentioned solution is inserted in the autoclave containing polytetrafluoroethyllining lining, 180 DEG C of constant temperature 48h of temperature, so
After naturally cool to room temperature；
1.3rd, the sample after cooling is inserted into centrifuge separation, then adds deionized water to pH value weakly acidic pH；
1.4th, the hydrochloric acid solution cleaning sample for being 0.1mol/L with concentration, then with deionized water cleaning sample to pH value it is near in
Property；
1.5th, separated using centrifuge, titania nanotube is obtained after 100 DEG C of dryings；
2nd, nitrogen Fe2O3 doping is carried out to titania nanotube
2.1st, the titania nanotube that step 1 is prepared is inserted in the iron nitrate solution that concentration is 0.2mol/L,
Soak 24h；
2.2nd, above-mentioned sample is inserted into tube furnace, maintains ammonia atmosphere, 500 DEG C of temperature heats 2h, obtains iron, nitrogen and is co-doped with
Miscellaneous titania nanotube；
3rd, bismuth tungstate titanium dioxide nanotube is prepared
3.1st, by Bi (NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution respectively, and mass fraction is respectively
0.5%wt and 0.4%wt, stirring is to being sufficiently mixed；
3.2nd, above-mentioned solution is moved into the hydrothermal reaction kettle containing teflon lined, and is put into step 2 wherein and made
The titania nanotube got ready, reaction naturally cools to room temperature after terminating；
3.3rd, sample deionized water and absolute ethyl alcohol are alternately rinsed 5 times, is then placed in drying box 50 DEG C and does
Dry 12h, you can bismuth tungstate titanium dioxide nanotube is made.
Present invention incorporates the method for ion doping and semiconductors coupling, Fe, N are adulterated and bismuth tungstate titanium dioxide is answered
Conjunction is combined, and on the one hand improves catalytic efficiency, on the other hand by the spectral response range of photochemical catalyst from the ultraviolet of below 387nm
Near infrared band is partially extended into, the response of nano titanium dioxide photocatalyst visible ray and near infrared light is realized, enhances
The catalytic activity of nanometer titanium dioxide carbon photochemical catalyst.
For the person of ordinary skill of the art, without departing from the concept of the premise of the invention, it can also do
Go out several modifications and improvements, these belong to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the photochemical catalyst of wide spectrum response, it is characterised in that the photochemical catalyst of the wide spectrum response
It is the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping, the preparation method of the photochemical catalyst of the wide spectrum response is such as
Under：
1) titanium dioxide nano material, is prepared；The titanium dioxide nano material is titania nanoparticles or titanium dioxide
Nanotube；
2) nitrogen Fe2O3 doping, is carried out to titanium dioxide nano material；
3) the bismuth tungstate composite titanium dioxide nano material of nitrogen Fe2O3 doping, is prepared.
2. the preparation method of the photochemical catalyst of wide spectrum response as claimed in claim 1, it is characterised in that the step 1)
In, nanometer titanium dioxide titanium nano particle can be prepared using vaporization condensation process, collosol and gel, hydro-thermal method, or using hydro-thermal method, template
Method, anodizing, crystal powder resolution method prepare titania nanotube.
3. the preparation method of the photochemical catalyst of wide spectrum response as claimed in claim 1, it is characterised in that the step 2) it is right
The method that titanium dioxide nano material carries out nitrogen Fe2O3 doping has steps of：
2.1), by step 1) titanium dioxide nano material for preparing inserts in iron nitrate solution, soaks；
2.2) above-mentioned material, is inserted into tube furnace, ammonia atmosphere is maintained, heating obtains the nano titania of Fe-Mn cycle and transference
Material.
4. the preparation method of the photochemical catalyst of wide spectrum response as claimed in claim 1, it is characterised in that the step 3) system
The step of bismuth tungstate composite titanium dioxide nano material of standby nitrogen Fe2O3 doping, is as follows：
3.1), by Bi (NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution respectively, and stirring is to being sufficiently mixed；
3.2), above-mentioned solution is moved into hydrothermal reaction kettle, and is put into step 2 wherein) the nano titania material for preparing
Material, reaction naturally cools to room temperature after terminating；
3.3), sample deionized water and absolute ethyl alcohol are alternately rinsed, is then placed in drying box and dries, you can nitrogen iron is made
The bismuth tungstate composite titanium dioxide nano material of doping.
5. the preparation method of the photochemical catalyst of wide spectrum response as claimed in claim 3, it is characterised in that the step 2.1)
The concentration of middle iron nitrate solution is 0.05~0.2mol/L.
6. the preparation method of the photochemical catalyst of wide spectrum response as claimed in claim 3, it is characterised in that the step 2.2)
The temperature of middle heating is 400~500 DEG C, heats 2~3h.
7. the preparation method of the photochemical catalyst of wide spectrum as claimed in claim 4 response, it is characterised in that step 3.1) in Bi
(NO3)3.5H2O and Na2WO4.2H2O is dissolved in ethylene glycol solution respectively, mass fraction be respectively 0.5~1%wt and 0.2~
0.4%wt.
8. a kind of photochemical catalyst of wide spectrum response, it is characterised in that the photochemical catalyst of the wide spectrum response is nitrogen Fe2O3 doping
Bismuth tungstate composite titanium dioxide nano material.
9. the photochemical catalyst of wide spectrum response as claimed in claim 8, it is characterised in that the bismuth tungstate of the nitrogen Fe2O3 doping is answered
Closing titanium dioxide nano material has following structure：Fe is with ferric form substitution tetravalence Ti4+It is present in TiO2In lattice, N
Replace O insertions TiO2Lattice, forms N-Ti-O networks.
10. the photochemical catalyst of wide spectrum response as claimed in claim 8, it is characterised in that the bismuth tungstate of the nitrogen Fe2O3 doping
In composite titanium dioxide nano material, wolframic acid bi content is 15~25%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111495435A (en) * | 2020-04-25 | 2020-08-07 | 河北工业大学 | Full-spectrum response photocatalytic filler and application thereof |
| CN115025769A (en) * | 2022-06-17 | 2022-09-09 | 暨南大学 | Photo-generated electron-thermal electron enhanced plasma photocatalyst and preparation method and application thereof |
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2017
- 2017-08-04 CN CN201710658538.5A patent/CN107321378A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 王波: "宽谱系光催化改性纳米TiO2的制备及其性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111495435A (en) * | 2020-04-25 | 2020-08-07 | 河北工业大学 | Full-spectrum response photocatalytic filler and application thereof |
| CN111495435B (en) * | 2020-04-25 | 2023-10-03 | 河北工业大学 | Full-spectrum response photocatalytic filler and application thereof |
| CN115025769A (en) * | 2022-06-17 | 2022-09-09 | 暨南大学 | Photo-generated electron-thermal electron enhanced plasma photocatalyst and preparation method and application thereof |
| CN115025769B (en) * | 2022-06-17 | 2024-03-22 | 暨南大学 | Photo-generated electron-hot electron enhanced plasma photocatalyst and preparation method and application thereof |
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