CN105036187B - Method for disordering transition metal oxide nanocrystallines through ultrasonic induction and product - Google Patents
Method for disordering transition metal oxide nanocrystallines through ultrasonic induction and product Download PDFInfo
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- CN105036187B CN105036187B CN201510441930.5A CN201510441930A CN105036187B CN 105036187 B CN105036187 B CN 105036187B CN 201510441930 A CN201510441930 A CN 201510441930A CN 105036187 B CN105036187 B CN 105036187B
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 39
- 230000006698 induction Effects 0.000 title abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 10
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 230000004941 influx Effects 0.000 claims description 7
- 230000005945 translocation Effects 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 25
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910003089 Ti–OH Inorganic materials 0.000 description 5
- 229910003077 Ti−O Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for disordering transition metal oxide nanocrystallines through ultrasonic induction and a product. Transition metal oxide nanocrystalline raw materials are dissolved in deionized water to obtain sol, ultrasonic processing is conducted on the sol, then disordered transition metal oxides are obtained through drying in an oven; compared with the raw materials not processed through ultrasonic waves, the disordered transition metal oxides are smaller in grain size, larger in hydroxyl content, higher in absorption, narrower in energy gap and better in photocatalytic performance. The transition metal oxide nanocrystalline raw materials include TiO2, ZnO, ZrO2, Fe2O3 and SnO2, and users can prepare the transition metal oxide nanocrystallines by themselves or directly purchase commercial nanocrystallines. The transition metal oxide nanocrystallines of transition metal oxides including TiO2, ZnO, ZrO2, Fe2O3, SnO2 and the like are disordered through the easy and convenient ultrasonic means, material modification is successfully achieved, deeper color, higher visible light absorption, smaller energy gap and higher photocatalytic property are expressed, and the application range of the disordering project is greatly widened.
Description
Technical field
The invention belongs to the modified field of metal oxide functional material, produce method and the product of disordering particularly to a kind of supersonic induced transition metal oxide.
Background technology
Nano-TiO2Due to photochemical reaction and the electron transport performance of its excellence, it is widely used in the field such as photocatalysis and DSSC.But, its conventional energy gap (3.2 ~ 3.7eV) makes it can only respond ultraviolet light, seriously limits its actual application.To TiO2The various metal of middle incorporation or nonmetallic heteroatoms can produce interband energy level so that it is energy gap narrows, but due to the impact of quantum size effect, its visible absorption is the most not enough.In recent years, TiO2Disordering engineering be suggested and extensive discussions.In general, TiO2The method of disordering many employings hydrogen treat, make TiO2Nanocrystal surface degree of hydroxylation raises, and induction produces disordered layer, and unordered coupling plays local band curvature, causes energy gap to narrow and visible absorption strengthens, and final result is nano-TiO2Macroscopic view color blackening, photocatalysis performance improves.Although to nano-TiO2Disordering engineering mechanism also have a lot of dispute, but great majority test result indicate that this is a nano-TiO2Modified effective way.But, the problems such as complicated, the with high costs and safety of operation is low that use hydrogen treat eventually to exist.Follow-up study has using plasma sputtering or aluminum reduction method induction nano-TiO2Disordering, also achieves good effect.
Many transition metal oxides are due to structure and TiO2Similar, also can have photocatalysis property, such as ZnO, ZrO2、Fe2O3And SnO2, but the research to these transition metal oxides does not has TiO2So extensively, and wherein the research about disordering engineering is more in blank.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides supersonic induced transition metal oxide nano crystalline substance and produce method and the product of disordering.
The technical solution used in the present invention is:
A kind of supersonic induced transition metal oxide nano crystalline substance produces the method for disordering, transition metal oxide nano crystalline substance material dissolution is obtained colloidal sol in deionized water, described colloidal sol is carried out supersound process, is dried to obtain the transition metal oxide of disordering the most in an oven；Described disordering transition metal oxide, the raw material before contrast echo, crystal grain reduces, hydroxy radical content increases, influx and translocation, energy gap narrow and photocatalysis performance improves.
Described transition metal oxide nano crystalline substance raw material includes TiO2、ZnO、ZrO2、Fe2O3And SnO2, self-control or directly purchase are commercial nanocrystalline.
Described supersound process, ultrasonic time 8 hours, power density 1500W/100mL, frequency 25kHz, carry out under 80 DEG C of constant temperatures.
Described dry temperature is 80 DEG C.
A kind of method described in any one obtains the transition metal oxide of disordering.
Beneficial effects of the present invention: the present invention is by TiO2 、ZnO、ZrO2、Fe2O3And SnO2Deng transition metal oxide, its nanocrystalline disordering is achieved by easy ultrasonic means, and it is successfully realized material modification, show deeper color, bigger visible absorption, narrower energy gap and higher photocatalytic activity, significantly expand the range of application of disordering engineering.Compared to prior art, more environmentally friendly, there is more preferable prospects for commercial application.Wherein ZnO, ZrO2、Fe2O3And SnO2The disordering brilliant Deng transition metal oxide nano is modified as first public.
Accompanying drawing explanation
Fig. 1 is sample photo before and after five kinds of transition metal oxide supersound process.After contrast can find supersound process, color sample is deepened；
Fig. 2 is the XRD figure spectrum of five kinds of transition metal oxides, and the sample crystallite dimension calculated after showing supersound process by Scherrer formula can be shunk；
Fig. 3 is the HRTEM photo of five kinds of transition metal oxides, and the sample crystalline surface after supersound process there will be unordered phase.Wherein Fe2O3Owing to magnetic cannot obtain photo to the impact of instrument；
Fig. 4 is the O 1s XPS photo of five kinds of transition metal oxides, the XPS spectrum of each sample can be decomposed into two Gaussian peaks, the Gaussian peak being wherein positioned at 528.1eV to 531.1eV represents X-O key, and another Gaussian peak being positioned at 530.9eV to 532eV represents X-OH key (X represents metallic atom).Being shown by the quantitative analysis of peak area, the sample degree of hydroxylation after supersound process raises；
Fig. 5 is the optical absorption spectra of five kinds of transition metal oxides, and the sample optical absorption intensity after supersound process can increase；
Fig. 6 is the VB XPS spectrum of five kinds of transition metal oxides, after indicating valence band location and the local band curvature of each sample respectively, and the position that top of valence band blue shift arrives；
Fig. 7 is the band structure schematic diagram of five kinds of transition metal oxides.There is local band curvature in the sample after supersound process, energy gap narrows；
Fig. 8 is that the kinetic rate of five kinds of transition metal oxide photocatalytic degradations magentas compares.Upper lower for b part for a part, a () sunlight catalytic energy is sufficiently large, its activity major influence factors is the combined efficiency of photo-generate electron-hole pair, sample surfaces disordered layer exists as defect, it it is the trap of photo-generated carrier, the compound of electron-hole pair can be greatly reduced, make sunlight catalytic activity improve.B () visible ray is relatively low due to excitation energy, it is necessary to making oxide energy gap meet certain condition could be catalyzed, and the sample energy gap of disordering narrows, and increases light-use, makes visible light catalytic performance improve.Wherein ZrO2And SnO2Visible light catalysis activity is not had owing to energy gap is excessive.It is much bigger that supersound process promotes degree comparison sunlight catalytic activity to the visible light catalysis activity of oxide.
Detailed description of the invention
Ultrasonic synthetic method can be used to stimulate the chemical process in liquid phase.When solution is by ultrasonic radiation, producing lockedin air space in solution, there is High Temperature High Pressure region in bubble center, here it is so-called acoustics hole.And ultrasonic primary chemical effect is just derived from quickly formation, growth and the process of avalanche of bubble in liquid phase.Low energy densities in sound field can be concentrated rapidly by this process, and the extreme condition of ultrasonic generation (local temperature > 5000K, pressure > 20MPa, cooldown rate > 1010Ks-1) impart the character that Solution Under Ultrasound Treatment is the most special, more discrete including making nanoparticle, it is thus achieved that bigger region, surface, more preferable thermodynamic stability and phase purity.Using aqueous phase one-step method to prepare presoma in Patent Application Publication (application number: 201410424413.2), and utilize ultrasonic being modified, that obtain is unformed TiO2.Present patent application directly carries out supersound process to ready-made transition metal oxide nano crystalline substance, require to reduce to presoma and (buy reagent, can synthesize without oneself control condition, simplify operating process, self-control can also be selected), and first the means of supersonic induced nanocrystalline disordering are applied to except TiO2On outer transition metal oxide.
Below in conjunction with embodiment, the present invention is elaborated.
Embodiment
1
By nanocrystalline for 0.1g TiO2(Degussa P25, Germany) it is dissolved in 100mL deionized water, put into the combination of XH-300UL computer microwave ultrasound wave ultraviolet light after stirring to catalyze and synthesize in instrument (Beijing XiangHu Science and Technology Development Co., Ltd.) and carry out supersound process, ultrasound condition is 80 DEG C of constant temperature, ultrasonic power density 1500W/100mL, frequency 25kHz, the time is 8 hours.Colloidal sol is put into be evaporated at 80 DEG C in baking oven after completing and is obtained sample TiO by process2-U(Fig. 1, Fig. 3).After test finds supersound process, TiO2Mean diameter narrows down to 18.98nm(Fig. 2 from 21.35nm), Ti-OH/Ti-O ratio increases to 0.65(Fig. 4 from 0.18), light influx and translocation (Fig. 5), top of valence band is blue shifted to 0.75eV(Fig. 6 by 2.58eV, Fig. 7), solar radiation photocatalytic degradation magenta efficiency improves 49%, it is seen that photocatalysis efficiency improves 266%(Fig. 8).
Embodiment
2
0.1g Nanocrystalline ZnO Powder (Aladdin reagent) is dissolved in 100mL deionized water, put into the combination of XH-300UL computer microwave ultrasound wave ultraviolet light after stirring to catalyze and synthesize instrument carries out supersound process, ultrasound condition is 80 DEG C of constant temperature, ultrasonic power density 1500W/100mL, frequency 25kHz, the time is 8 hours.Colloidal sol is put into be evaporated at 80 DEG C in baking oven after completing and is obtained sample ZnO-U(Fig. 1, Fig. 3 by process).After test finds supersound process, ZnO mean diameter narrows down to 16.15nm(Fig. 2 from 17.09nm), Ti-OH/Ti-O ratio increases to 0.98(Fig. 4 from 0.68), light influx and translocation (Fig. 5), top of valence band is blue shifted to 1.46eV(Fig. 6 by 2.54eV, Fig. 7), solar radiation photocatalytic degradation magenta efficiency improves 27%, it is seen that photocatalysis efficiency improves 239%(Fig. 8).
Embodiment
3
By nanocrystalline for 0.1g ZrO2(Shanghai Mai Kun Chemical Co., Ltd.) is dissolved in 100mL deionized water, put into the combination of XH-300UL computer microwave ultrasound wave ultraviolet light after stirring to catalyze and synthesize instrument carries out supersound process, ultrasound condition is 80 DEG C of constant temperature, ultrasonic power density 1500W/100mL, frequency 25kHz, the time is 8 hours.Colloidal sol is put into be evaporated at 80 DEG C in baking oven after completing and is obtained sample ZrO by process2-U(Fig. 1, Fig. 3).After test finds supersound process, ZrO2Mean diameter narrows down to 27.09nm(Fig. 2 from 28.18nm), Ti-OH/Ti-O ratio increases to 0.96(Fig. 4 from 0.57), light influx and translocation (Fig. 5), top of valence band is blue shifted to 1.76eV(Fig. 6 by 2.70eV, Fig. 7), solar radiation photocatalytic degradation magenta efficiency improves 43%(Fig. 8).
Embodiment
4
By 0.1g nano-crystalline Fe2O3(Changsha Jing Kang new material Science and Technology Ltd.) is dissolved in 100mL deionized water, put into the combination of XH-300UL computer microwave ultrasound wave ultraviolet light after stirring to catalyze and synthesize instrument carries out supersound process, ultrasound condition is 80 DEG C of constant temperature, ultrasonic power density 1500W/100mL, frequency 25kHz, the time is 8 hours.Colloidal sol is put into be evaporated at 80 DEG C in baking oven after completing and is obtained sample F e by process2O3-U(Fig. 1, Fig. 3).After test finds supersound process, Fe2O3Mean diameter narrows down to 14.68nm(Fig. 2 from 15.78nm), Ti-OH/Ti-O ratio increases to 0.98(Fig. 4 from 0.34), light influx and translocation (Fig. 5), top of valence band is blue shifted to-0.58eV(Fig. 6 by 0.81eV, Fig. 7), solar radiation photocatalytic degradation magenta efficiency improves 46%, it is seen that photocatalysis efficiency improves 106%(Fig. 8).
Embodiment
5
By nanocrystalline for 0.1g SnO2(Aladdin reagent) is dissolved in 100mL deionized water, put into the combination of XH-300UL computer microwave ultrasound wave ultraviolet light after stirring to catalyze and synthesize instrument carries out supersound process, ultrasound condition is 80 DEG C of constant temperature, ultrasonic power density 1500W/100mL, frequency 25kHz, and the time is 8 hours.Colloidal sol is put into be evaporated at 80 DEG C in baking oven after completing and is obtained sample SnO by process2-U(Fig. 1, Fig. 3).After test finds supersound process, SnO2Mean diameter narrows down to 32.95nm(Fig. 2 from 33.64nm), Ti-OH/Ti-O ratio increases to 0.93(Fig. 4 from 0.66), light influx and translocation (Fig. 5), top of valence band is blue shifted to 2.96eV(Fig. 6 by 3.61eV, Fig. 7), solar radiation photocatalytic degradation magenta efficiency improves 76%(Fig. 8).
Claims (3)
1. the method that a supersonic induced transition metal oxide nano crystalline substance produces disordering, it is characterized in that, transition metal oxide nano crystalline substance material dissolution is obtained colloidal sol in deionized water, described colloidal sol is carried out supersound process, is dried to obtain the transition metal oxide of disordering the most in an oven；Described disordering transition metal oxide, the raw material before contrast echo, crystal grain reduces, hydroxy radical content increases, influx and translocation, energy gap narrow and photocatalysis performance improves；
The described transition metal oxide nano crystalline substance raw material described in transition metal oxide nano crystalline substance raw material is ZnO, ZrO2And Fe2O3One of them or compositions, self-control or directly to buy commercialization nanocrystalline；
Described supersound process, ultrasonic time 8 hours, power density 1500W/100mL, frequency 25kHz, carry out under 80 DEG C of constant temperatures.
Method the most according to claim 1, it is characterised in that described dry temperature is 80 DEG C.
3. a method according to claim 1 and 2 obtains the transition metal oxide of disordering.
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| CN104229876B (en) * | 2014-08-27 | 2015-11-11 | 浙江大学 | A kind of unformed hydroxylation nano-TiO of different blackness 2and preparation method thereof |
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