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, obtained Nd doping Bi
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 in container, adds water be mixed with mixed solution, and is stirred by mixed solution;
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
ndbe respectively the mole of Bi and Nd, reactant liquor is at room temperature stirred, obtain 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 after being incubated 30min-120min at 160 DEG C-220 DEG C;
Step 4: after question response temperature is down to room temperature, takes out microwave hydrothermal reaction kettle, isolates sediment wherein, then by sediment washing, ultrasonic disperse, 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.
Set microwave reaction instrument in described step 3 from room temperature to 100 DEG C, often heat up 50 DEG C of insulation 8min from 100 DEG C, until temperature is raised to 160 DEG C-220 DEG C.
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 for deionized water and absolute ethyl alcohol respectively by sediment washing repeatedly to sediment in neutral, and carry out next time again through the natural sedimentation of a day after each washing and wash.
The time of the ultrasonic disperse in described step 4 is 30-60min.
The baking temperature of the freeze-day with constant temperature in described step 4 is 75-85 DEG C, and drying time is 12-24 hour.
Described rare earth element nd doping Bi
2wO
6the rare earth element nd doping Bi that the preparation method of composite photo-catalyst obtains
2wO
6composite photo-catalyst, its main component is the Bi of orthorhombic phase
2wO
6, and Bi
2wO
6in containing Nd
3+, wherein the content of Nd is R
nd=2%-20%, and its pattern is for 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 obtains
2wO
6the application of composite photo-catalyst in 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, improves pure Bi
2wO
6the efficiency of photocatalysis to degrade organic matter under visible light.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 are 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 regular appearance, purity are higher, has visible light-responded performance, and be a kind of visible light responsible photocatalytic material with high catalytic activity, its main component is Bi
2wO
6, and Bi
2wO
6in containing Nd
3+, its pattern is the structure being self-assembled into class flower pattern by nanometer sheet.Rare earth element nd doping Bi provided by the invention
2wO
6composite photo-catalyst has good visible light photocatalysis active, the Bi that do not adulterate that the photocatalytic activity under its visible ray is obtained under the same terms
2wO
6photocatalytic activity, improve pure phase Bi
2wO
6the problem that catalytic efficiency is low, can be used in degradation of organic substances, has a good application prospect.
Detailed description of the invention
Be described further the present invention below in conjunction with accompanying drawing and the preferred embodiment of the invention, 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 in beaker, adds deionized water be mixed with mixed solution, 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 makes raw material wherein mix;
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), obtain precursor liquid by after reactant liquor at room temperature magnetic agitation 40min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio 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 to 100 DEG C, often heat up 50 DEG C of insulation 8min from 100 DEG C, until temperature is raised to 180 DEG C, stops reaction after being incubated 90min at 180 DEG C;
Step 4: after question response temperature is down to room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, after respectively sediment washing being repeatedly neutrality to sediment with deionized water and absolute ethyl alcohol (carrying out next time again through the natural sedimentation of a day after each washing to wash), ultrasonic disperse 60min again, again 80 DEG C of freeze-day with constant temperature 12 hours, obtain rare earth element nd doping Bi
2wO
6composite photo-catalyst.
Obtained rare earth element nd doping Bi
2wO
6composite photo-catalyst, its main component is the Bi of orthorhombic phase
2wO
6, and Bi
2wO
6in containing Nd
3+, wherein the content of Nd is R
nd=6%, and its pattern is the structure being self-assembled into class flower pattern 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 in beaker, adds 60ml deionized water be mixed with mixed solution, 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 makes raw material wherein mix;
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), obtain precursor liquid by after reactant liquor at room temperature magnetic agitation 40min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio 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 to 100 DEG C, often heat up 50 DEG C of insulation 8min from 100 DEG C, until temperature is raised to 200 DEG C, stops reaction after being incubated 120min at 200 DEG C;
Step 4: after question response temperature is down to room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, after respectively sediment washing being repeatedly neutrality to sediment with deionized water and absolute ethyl alcohol (carrying out next time again through the natural sedimentation of a day after each washing to wash), ultrasonic disperse 60min again, again 80 DEG C of freeze-day with constant temperature 12 hours, obtain rare earth element nd doping Bi
2wO
6composite photo-catalyst.
Obtained rare earth element nd doping Bi
2wO
6composite photo-catalyst, its main component is the Bi of orthorhombic phase
2wO
6, and Bi
2wO
6in containing Nd
3+, wherein the content of Nd is R
nd=10%, and its pattern is the structure being self-assembled into class flower pattern by nanometer sheet.
Fig. 1 is rare earth element nd doping Bi prepared by the embodiment of the present invention 2
2wO
6the XRD figure of composite photo-catalyst, as can be seen from the figure, Nd adulterates Bi
2wO
6all diffraction maximums of composite photo-catalyst are consistent with PDF card (JCPDS NO.39-0256), are orthorhombic phase Bi
2wO
6structure, other impurity phases are not introduced in the doping of Nd.
Fig. 2 is rare earth element nd doping Bi prepared by the embodiment of the present invention 2
2wO
6the SEM figure of composite photo-catalyst, as can be seen from the figure, the Nd doping Bi of preparation
2wO
6composite photo-catalyst is made up of nanometer sheet, and these nanometer sheet are self-assembled into the structure of similar flower pattern.
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 is unadulterated Bi respectively
2wO
6with rare earth element nd doping Bi prepared by embodiment 2
2wO
6composite photo-catalyst to the degradation rate curve of organic degradation thing rhodamine B, ordinate A/A
0for the ratio of the concentration after certain rhodamine B degraded and its initial concentration in moment, wherein unadulterated Bi
2wO
6be according to method of the present invention, undope Nd (NO in step 2
3)
36H
2o obtains.As can be seen from the figure, the rare earth element nd doping Bi of embodiment 2 preparation
2wO
6composite photo-catalyst has very high photocatalysis performance, significantly improves the degradation rate of rhodamine B, and during 90min, its degradation rate is increased to 90% by by 60% when undoping, and rare earth element nd provided by the invention doping Bi is described
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 in beaker, adds deionized water be mixed with mixed solution, 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 makes raw material wherein mix;
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), obtain precursor liquid by after reactant liquor at room temperature magnetic agitation 20min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio 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 to 100 DEG C, often heat up 50 DEG C of insulation 8min from 100 DEG C, until temperature is raised to 220 DEG C, stops reaction after being incubated 60min at 220 DEG C;
Step 4: after question response temperature is down to room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, after respectively sediment washing being repeatedly neutrality to sediment with deionized water and absolute ethyl alcohol (carrying out next time again through the natural sedimentation of a day after each washing to wash), ultrasonic disperse 30min again, again 75 DEG C of freeze-day with constant temperature 24 hours, obtain rare earth element nd doping Bi
2wO
6composite photo-catalyst.
Obtained rare earth element nd doping Bi
2wO
6composite photo-catalyst, its main component is the Bi of orthorhombic phase
2wO
6, and Bi
2wO
6in containing Nd
3+, wherein the content of Nd is R
nd=15%, and its pattern is the structure being self-assembled into class flower pattern 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 in beaker, adds deionized water be mixed with mixed solution, 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 makes raw material wherein mix;
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), obtain precursor liquid by after reactant liquor at room temperature magnetic agitation 40min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio 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 to 100 DEG C, often heat up 50 DEG C of insulation 8min from 100 DEG C, until temperature is raised to 160 DEG C, stops reaction after being incubated 30min at 160 DEG C;
Step 4: after question response temperature is down to room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, after respectively sediment washing being repeatedly neutrality to sediment with deionized water and absolute ethyl alcohol (carrying out next time again through the natural sedimentation of a day after each washing to wash), ultrasonic disperse 40min again, again 85 DEG C of freeze-day with constant temperature 12 hours, obtain rare earth element nd doping Bi
2wO
6composite photo-catalyst.
Obtained rare earth element nd doping Bi
2wO
6composite photo-catalyst, its main component is the Bi of orthorhombic phase
2wO
6, and Bi
2wO
6in containing Nd
3+, wherein the content of Nd is R
nd=18%, and its pattern is the structure being self-assembled into class flower pattern 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 in beaker, adds deionized water be mixed with mixed solution, 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 makes raw material wherein mix;
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), obtain precursor liquid by after reactant liquor at room temperature magnetic agitation 30min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio 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 to 100 DEG C, often heat up 50 DEG C of insulation 8min from 100 DEG C, until temperature is raised to 190 DEG C, stops reaction after being incubated 50min at 190 DEG C;
Step 4: after question response temperature is down to room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, after respectively sediment washing being repeatedly neutrality to sediment with deionized water and absolute ethyl alcohol (carrying out next time again through the natural sedimentation of a day after each washing to wash), ultrasonic disperse 50min again, again 80 DEG C of freeze-day with constant temperature 16 hours, obtain rare earth element nd doping Bi
2wO
6composite photo-catalyst.
Obtained rare earth element nd doping Bi
2wO
6composite photo-catalyst, its main component is the Bi of orthorhombic phase
2wO
6, and Bi
2wO
6in containing Nd
3+, wherein the content of Nd is R
nd=2%, and its pattern is the structure being self-assembled into class flower pattern 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 in beaker, adds deionized water be mixed with mixed solution, 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 makes raw material wherein mix;
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), obtain precursor liquid by after reactant liquor at room temperature magnetic agitation 40min;
Step 3: precursor liquid is moved in teflon-lined microwave hydrothermal reaction kettle, the packing ratio 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 to 100 DEG C, often heat up 50 DEG C of insulation 8min from 100 DEG C, until temperature is raised to 170 DEG C, stops reaction after being incubated 100min at 170 DEG C;
Step 4: after question response temperature is down to room temperature, take out microwave hydrothermal reaction kettle, isolate sediment wherein, after respectively sediment washing being repeatedly neutrality to sediment with deionized water and absolute ethyl alcohol (carrying out next time again through the natural sedimentation of a day after each washing to wash), ultrasonic disperse 45min again, again 75 DEG C of freeze-day with constant temperature 20 hours, obtain rare earth element nd doping Bi
2wO
6composite photo-catalyst.
Obtained rare earth element nd doping Bi
2wO
6composite photo-catalyst, its main component is the Bi of orthorhombic phase
2wO
6, and Bi
2wO
6in containing Nd
3+, wherein the content of Nd is R
nd=20%, and its pattern is the structure being self-assembled into class flower pattern by nanometer sheet.
The foregoing is only one embodiment of the present invention, it not whole or unique embodiment, the conversion of those of ordinary skill in the art by reading description of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.