Summary of the invention
The object of the present invention is to provide a kind of rare earth element nd doping Bi
2wO
6composite photo-catalyst and its preparation method and application, this preparation method's reaction time is short, and technological process is simple, the Nd doping Bi making
2wO
6composite photo-catalyst possesses good photocatalytic activity.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of rare earth element nd doping Bi
2wO
6the preparation method of composite photo-catalyst, comprises the following steps:
Step 1: by Bi (NO
3)
35H
2o and Na
2wO
42H
2o puts into container according to the mol ratio of Bi:W=2:1, then adds water to be mixed with mixed solution in container, and mixed solution is stirred;
Step 2: by Nd (NO
3)
36H
2o joins in mixed solution, obtains reactant liquor, wherein the addition R of Nd
nd=2%-20%, R
nd=n
nd/ (n
bi+ n
nd) * 100%, n
biand n
ndthe mole that is respectively Bi and Nd, at room temperature stirs reactant liquor, obtains precursor liquid;
Step 3: precursor liquid is moved in microwave hydrothermal reaction kettle, then microwave hydrothermal reaction kettle is put into microwave hydrothermal reaction, setting power is 300W, stops reaction at 160 ℃-220 ℃ after being incubated 30min-120min;
Step 4: question response temperature is down to after room temperature, takes out microwave hydrothermal reaction kettle, isolates sediment wherein, then by sediment washing, ultrasonic dispersion, freeze-day with constant temperature, obtains rare earth element nd doping Bi
2wO
6composite photo-catalyst.
Bi (NO in the mixed solution of described step 1
3)
35H
2the concentration of O is 0.1mol/L-0.6mol/L, Na
2wO
42H
2the concentration of O is 0.05mol/L-0.3mol/L.
The required time that stirs in described step 2 is 20-40min.
In described step 3, set microwave reaction instrument and be warming up to 100 ℃ from room temperature, 50 ℃ of insulation 8min of every intensification from 100 ℃, until temperature is raised to 160 ℃-220 ℃.
In described step 3, the packing ratio of microwave hydrothermal reaction kettle is 40%-70%, and the liner of microwave hydrothermal reaction kettle is polytetrafluoroethylene (PTFE) material.
Washing in described step 4 is respectively sediment washing to be repeatedly to neutral to sediment with deionized water and absolute ethyl alcohol, and after each washing, through the natural sedimentation of a day, carries out next time again and wash.
The time of the ultrasonic dispersion in described step 4 is 30-60min.
The baking temperature of the freeze-day with constant temperature in described step 4 is 75-85 ℃, and be 12-24 hour drying time.
Described rare earth element nd doping Bi
2wO
6the rare earth element nd doping Bi that the preparation method of composite photo-catalyst makes
2wO
6composite photo-catalyst, its main component is the Bi of quadrature phase
2wO
6, and Bi
2wO
6in contain Nd
3+, wherein the content of Nd is R
nd=2%-20%, and its pattern is for to be self-assembled into flower type structure by nanometer sheet.
Described rare earth element nd doping Bi
2wO
6the rare earth element nd doping Bi that the preparation method of composite photo-catalyst makes
2wO
6the application of composite photo-catalyst aspect degradation of organic substances.
Compared with prior art, the present invention has following beneficial effect:
Rare earth element nd doping Bi provided by the invention
2wO
6the preparation method of composite photo-catalyst, with five water bismuth nitrate (Bi (NO
3)
35H
2o) be Bi source, tungstate dihydrate acid sodium (Na
2wO
42H
2o) be W source, according to the mol ratio of Bi:W=2:1 by its preparation Bi soluble in water
2wO
6, then add six water neodymium nitrate (Nd (NO
3)
36H
2o), to Bi
2wO
6carry out Nd
3+doping, by microwave-hydrothermal method by Nd
3+introduce Bi
2wO
6in, prepare rare earth element nd doping Bi
2wO
6composite photo-catalyst, has improved pure Bi
2wO
6the efficiency of photocatalysis to degrade organic matter under visible ray.The microwave-hydrothermal method that the present invention adopts combines the heat characteristic of microwave uniqueness and the advantage of hydro-thermal method, do not need to add other additive, one-step synthesis product, reaction speed is fast, generated time is short, reaction condition is gentle, reaction efficiency is high, environmental friendliness, technique is simple and easy to control, manufacturing cycle is short, save the energy.
Rare earth element nd doping Bi provided by the invention
2wO
6composite photo-catalyst is orthorhombic phase structure, and pattern is regular, purity is higher, has visible light-responded performance, is a kind of visible light responsible photocatalytic material with high catalytic activity, and its main component is Bi
2wO
6, and Bi
2wO
6in contain Nd
3+, its pattern is for being self-assembled into the structure of class flower type by nanometer sheet.Rare earth element nd doping Bi provided by the invention
2wO
6composite photo-catalyst has good visible light photocatalysis active, and the photocatalytic activity under its visible ray is apparently higher than the not doping Bi making under the same terms
2wO
6photocatalytic activity, improved pure phase Bi
2wO
6the problem that catalytic efficiency is low, can be used in degradation of organic substances, has a good application prospect.
The specific embodiment
Below in conjunction with accompanying drawing and the preferred embodiment of the invention, the present invention is described further, it is pure that raw material is analysis.
Embodiment 1:
Rare earth element nd doping Bi
2wO
6the preparation method of composite photo-catalyst, comprises the following steps:
Step 1: take Bi (NO according to the mol ratio of Bi:W=2:1
3)
35H
2o and Na
2wO
42H
2o puts into beaker, then adds deionized water to be mixed with mixed solution in beaker, wherein Bi (NO
3)
35H
2the concentration of O is 0.2mol/L, Na
2wO
42H
2the concentration of O is 0.1mol/L, and magnetic agitation mixed solution 40min mixes raw material wherein;
Step 2: take a certain amount of Nd (NO
3)
36H
2o joins in mixed solution, obtains reactant liquor, wherein the addition R of Nd
nd=6%(R
nd=n
nd/ (n
bi+ n
nd) * 100%, n
biand n
ndbe respectively the mole of Bi and Nd), reactant liquor is at room temperature obtained to precursor liquid after magnetic agitation 40min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 40%, again microwave hydrothermal reaction kettle is put into microwave hydrothermal reaction, setting power is 300W, from room temperature, be warming up to 100 ℃, 50 ℃ of every intensifications insulation 8min from 100 ℃, until temperature is raised to 180 ℃, stop reaction after being incubated 90min at 180 ℃;
Step 4: question response temperature is down to after room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, with deionized water and absolute ethyl alcohol, respectively sediment washing is repeatedly after neutrality and (after each washing, through the natural sedimentation of a day, carries out washing next time again) to sediment, ultrasonic dispersion 60min again, 80 ℃ of freeze-day with constant temperature 12 hours, obtain rare earth element nd doping Bi again
2wO
6composite photo-catalyst.
The rare earth element nd doping Bi making
2wO
6composite photo-catalyst, its main component is the Bi of quadrature phase
2wO
6, and Bi
2wO
6in contain Nd
3+, wherein the content of Nd is R
nd=6%, and its pattern is for being self-assembled into the structure of class flower type by nanometer sheet.
Embodiment 2:
Rare earth element nd doping Bi
2wO
6the preparation method of composite photo-catalyst, comprises the following steps:
Step 1: take Bi (NO according to the mol ratio of Bi:W=2:1
3)
35H
2o and Na
2wO
42H
2o puts into beaker, then adds 60ml deionized water to be mixed with mixed solution in beaker, wherein Bi (NO
3)
35H
2the concentration of O is 0.1mol/L, Na
2wO
42H
2the concentration of O is 0.05mol/L, and magnetic agitation mixed solution 40min mixes raw material wherein;
Step 2: take a certain amount of Nd (NO
3)
36H
2o joins in mixed solution, obtains reactant liquor, wherein the addition R of Nd
nd=10%(R
nd=n
nd/ (n
bi+ n
nd) * 100%, n
biand n
ndbe respectively the mole of Bi and Nd), reactant liquor is at room temperature obtained to precursor liquid after magnetic agitation 40min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 60%, again microwave hydrothermal reaction kettle is put into microwave hydrothermal reaction, setting power is 300W, from room temperature, be warming up to 100 ℃, 50 ℃ of every intensifications insulation 8min from 100 ℃, until temperature is raised to 200 ℃, stop reaction after being incubated 120min at 200 ℃;
Step 4: question response temperature is down to after room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, with deionized water and absolute ethyl alcohol, respectively sediment washing is repeatedly after neutrality and (after each washing, through the natural sedimentation of a day, carries out washing next time again) to sediment, ultrasonic dispersion 60min again, 80 ℃ of freeze-day with constant temperature 12 hours, obtain rare earth element nd doping Bi again
2wO
6composite photo-catalyst.
The rare earth element nd doping Bi making
2wO
6composite photo-catalyst, its main component is the Bi of quadrature phase
2wO
6, and Bi
2wO
6in contain Nd
3+, wherein the content of Nd is R
nd=10%, and its pattern is for being self-assembled into the structure of class flower type by nanometer sheet.
Fig. 1 is the rare earth element nd doping Bi of the embodiment of the present invention 2 preparations
2wO
6the XRD figure of composite photo-catalyst, as can be seen from the figure, the Nd Bi that adulterates
2wO
6all diffraction maximums of composite photo-catalyst are consistent with PDF card (JCPDS NO.39-0256), are quadrature phase Bi
2wO
6structure, other impurity phases are not introduced in the doping of Nd.
Fig. 2 is the rare earth element nd doping Bi of the embodiment of the present invention 2 preparations
2wO
6the SEM figure of composite photo-catalyst, as can be seen from the figure, the Nd of the preparation Bi that adulterates
2wO
6composite photo-catalyst consists of nanometer sheet, and these nanometer sheet are self-assembled into the structure of class floweriness type.
Fig. 3 is rare earth element nd doping Bi prepared by the present invention
2wO
6the degradation rate curve of composite photo-catalyst, in figure, a, b curve are respectively unadulterated Bi
2wO
6rare earth element nd doping Bi with embodiment 2 preparations
2wO
6the degradation rate curve of composite photo-catalyst to organic degradation thing rhodamine B, ordinate A/A
0for concentration and the ratio of its initial concentration, the wherein unadulterated Bi after certain rhodamine B degraded constantly
2wO
6be according to method of the present invention, Nd (NO undopes in step 2
3)
36H
2o obtains.As can be seen from the figure, the rare earth element nd doping Bi of embodiment 2 preparations
2wO
6composite photo-catalyst has very high photocatalysis performance, has obviously improved the degradation rate of rhodamine B, and during 90min, its degradation rate, by 60% being increased to 90% when undoping, illustrates rare earth element nd doping Bi provided by the invention
2wO
6composite photo-catalyst has good visible light photocatalysis active, can be used in degradation of organic substances.。
Embodiment 3
Rare earth element nd doping Bi
2wO
6the preparation method of composite photo-catalyst, comprises the following steps:
Step 1: take Bi (NO according to the mol ratio of Bi:W=2:1
3)
35H
2o and Na
2wO
42H
2o puts into beaker, then adds deionized water to be mixed with mixed solution in beaker, wherein Bi (NO
3)
35H
2the concentration of O is 0.6mol/L, Na
2wO
42H
2the concentration of O is 0.3mol/L, and magnetic agitation mixed solution 40min mixes raw material wherein;
Step 2: take a certain amount of Nd (NO
3)
36H
2o joins in mixed solution, obtains reactant liquor, wherein the addition R of Nd
nd=15%(R
nd=n
nd/ (n
bi+ n
nd) * 100%, n
biand n
ndbe respectively the mole of Bi and Nd), reactant liquor is at room temperature obtained to precursor liquid after magnetic agitation 20min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 70%, again microwave hydrothermal reaction kettle is put into microwave hydrothermal reaction, setting power is 300W, from room temperature, be warming up to 100 ℃, 50 ℃ of every intensifications insulation 8min from 100 ℃, until temperature is raised to 220 ℃, stop reaction after being incubated 60min at 220 ℃;
Step 4: question response temperature is down to after room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, with deionized water and absolute ethyl alcohol, respectively sediment washing is repeatedly after neutrality and (after each washing, through the natural sedimentation of a day, carries out washing next time again) to sediment, ultrasonic dispersion 30min again, 75 ℃ of freeze-day with constant temperature 24 hours, obtain rare earth element nd doping Bi again
2wO
6composite photo-catalyst.
The rare earth element nd doping Bi making
2wO
6composite photo-catalyst, its main component is the Bi of quadrature phase
2wO
6, and Bi
2wO
6in contain Nd
3+, wherein the content of Nd is R
nd=15%, and its pattern is for being self-assembled into the structure of class flower type by nanometer sheet.
Embodiment 4
Rare earth element nd doping Bi
2wO
6the preparation method of composite photo-catalyst, comprises the following steps:
Step 1: take Bi (NO according to the mol ratio of Bi:W=2:1
3)
35H
2o and Na
2wO
42H
2o puts into beaker, then adds deionized water to be mixed with mixed solution in beaker, wherein Bi (NO
3)
35H
2the concentration of O is 0.4mol/L, Na
2wO
42H
2the concentration of O is 0.2mol/L, and magnetic agitation mixed solution 40min mixes raw material wherein;
Step 2: take a certain amount of Nd (NO
3)
36H
2o joins in mixed solution, obtains reactant liquor, wherein the addition R of Nd
nd=18%(R
nd=n
nd/ (n
bi+ n
nd) * 100%, n
biand n
ndbe respectively the mole of Bi and Nd), reactant liquor is at room temperature obtained to precursor liquid after magnetic agitation 40min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 50%, again microwave hydrothermal reaction kettle is put into microwave hydrothermal reaction, setting power is 300W, from room temperature, be warming up to 100 ℃, 50 ℃ of every intensifications insulation 8min from 100 ℃, until temperature is raised to 160 ℃, stop reaction after being incubated 30min at 160 ℃;
Step 4: question response temperature is down to after room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, with deionized water and absolute ethyl alcohol, respectively sediment washing is repeatedly after neutrality and (after each washing, through the natural sedimentation of a day, carries out washing next time again) to sediment, ultrasonic dispersion 40min again, 85 ℃ of freeze-day with constant temperature 12 hours, obtain rare earth element nd doping Bi again
2wO
6composite photo-catalyst.
The rare earth element nd doping Bi making
2wO
6composite photo-catalyst, its main component is the Bi of quadrature phase
2wO
6, and Bi
2wO
6in contain Nd
3+, wherein the content of Nd is R
nd=18%, and its pattern is for being self-assembled into the structure of class flower type by nanometer sheet.
Embodiment 5
Rare earth element nd doping Bi
2wO
6the preparation method of composite photo-catalyst, comprises the following steps:
Step 1: take Bi (NO according to the mol ratio of Bi:W=2:1
3)
35H
2o and Na
2wO
42H
2o puts into beaker, then adds deionized water to be mixed with mixed solution in beaker, wherein Bi (NO
3)
35H
2the concentration of O is 0.3mol/L, Na
2wO
42H
2the concentration of O is 0.15mol/L, and magnetic agitation mixed solution 40min mixes raw material wherein;
Step 2: take a certain amount of Nd (NO
3)
36H
2o joins in mixed solution, obtains reactant liquor, wherein the addition R of Nd
nd=2%(R
nd=n
nd/ (n
bi+ n
nd) * 100%, n
biand n
ndbe respectively the mole of Bi and Nd), reactant liquor is at room temperature obtained to precursor liquid after magnetic agitation 30min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 55%, again microwave hydrothermal reaction kettle is put into microwave hydrothermal reaction, setting power is 300W, from room temperature, be warming up to 100 ℃, 50 ℃ of every intensifications insulation 8min from 100 ℃, until temperature is raised to 190 ℃, stop reaction after being incubated 50min at 190 ℃;
Step 4: question response temperature is down to after room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, with deionized water and absolute ethyl alcohol, respectively sediment washing is repeatedly after neutrality and (after each washing, through the natural sedimentation of a day, carries out washing next time again) to sediment, ultrasonic dispersion 50min again, 80 ℃ of freeze-day with constant temperature 16 hours, obtain rare earth element nd doping Bi again
2wO
6composite photo-catalyst.
The rare earth element nd doping Bi making
2wO
6composite photo-catalyst, its main component is the Bi of quadrature phase
2wO
6, and Bi
2wO
6in contain Nd
3+, wherein the content of Nd is R
nd=2%, and its pattern is for being self-assembled into the structure of class flower type by nanometer sheet.
Embodiment 6
Rare earth element nd doping Bi
2wO
6the preparation method of composite photo-catalyst, comprises the following steps:
Step 1: take Bi (NO according to the mol ratio of Bi:W=2:1
3)
35H
2o and Na
2wO
42H
2o puts into beaker, then adds deionized water to be mixed with mixed solution in beaker, wherein Bi (NO
3)
35H
2the concentration of O is 0.5mol/L, Na
2wO
42H
2the concentration of O is 0.25mol/L, and magnetic agitation mixed solution 40min mixes raw material wherein;
Step 2: take a certain amount of Nd (NO
3)
36H
2o joins in mixed solution, obtains reactant liquor, wherein the addition R of Nd
nd=20%(R
nd=n
nd/ (n
bi+ n
nd) * 100%, n
biand n
ndbe respectively the mole of Bi and Nd), reactant liquor is at room temperature obtained to precursor liquid after magnetic agitation 40min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio of controlling microwave hydrothermal reaction kettle is 65%, again microwave hydrothermal reaction kettle is put into microwave hydrothermal reaction, setting power is 300W, from room temperature, be warming up to 100 ℃, 50 ℃ of every intensifications insulation 8min from 100 ℃, until temperature is raised to 170 ℃, stop reaction after being incubated 100min at 170 ℃;
Step 4: question response temperature is down to after room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, with deionized water and absolute ethyl alcohol, respectively sediment washing is repeatedly after neutrality and (after each washing, through the natural sedimentation of a day, carries out washing next time again) to sediment, ultrasonic dispersion 45min again, 75 ℃ of freeze-day with constant temperature 20 hours, obtain rare earth element nd doping Bi again
2wO
6composite photo-catalyst.
The rare earth element nd doping Bi making
2wO
6composite photo-catalyst, its main component is the Bi of quadrature phase
2wO
6, and Bi
2wO
6in contain Nd
3+, wherein the content of Nd is R
nd=20%, and its pattern is for being self-assembled into the structure of class flower type by nanometer sheet.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading description of the present invention, is claim of the present invention and contains.