A kind of Fe3O4-C@Bi2O3-BiOI photocatalyst and its preparation method and application
Technical field
The present invention relates to catalysis material technical field, especially visible light responsible photocatalytic material technical field, specifically
Relate to a kind of Fe3O4-C@Bi2O3-BiOI photocatalyst and preparation method thereof.
Background technology
Photocatalyst technology is using the reaction of its normal-temperature deep and can directly utilize solar energy as light source to drive the spies such as reaction
Property so that it is at aspects such as the depollutions of environment, there is broad based growth prospect.With TiO2For represent photocatalyst ultraviolet light irradiate under
Photo-generate electron-hole pair can be produced, it is possible to achieve the heavy metal ion in environment is removed/reclaimed to reduction reaction.But it is the most sharp
With accounting for the less ultraviolet region of sunlight gross energy.Further, since photocatalyst can be recycled, market is widely used, powder body
The recovery of photocatalyst and stability just seem particularly significant.Thus, on the premise of keeping photocatalyst activity, preparation one
The recyclable photocatalyst of high visible response has the highest using value.
Bismuth system catalysis material is because of its narrower energy gap, it is possible to utilize visible ray to cause people greatly to pay close attention to.Oxygen
Changing bismuth band-gap energy is 2.6~2.8eV, and absorbing wavelength is longer, has certain utilization rate to visible ray;BiOX, is a kind of new
Type, there is the bismuth system catalysis material of excellent photocatalytic activity, wherein, Basic bismuth iodide is minimum due to band gap, inhales visible ray
Receive height, be a kind of visible-light photocatalyst material having a extensive future.By semiconductors coupling method, by bismuth oxide and BiOX
In conjunction with, hetero-junctions can be formed, improve catalyst further visible light-responded, thus improve heavy metal containing wastewater treatment effect.Four
Fe 3 O, as a kind of multifunction magnetic material, at necks such as the treatment of tumor, microwave absorbing material, catalyst carrier medicine
Territory is widely used the most, has good development prospect.
Summary of the invention
The invention provides a kind of Fe3O4-C@Bi2O3-BiOI photocatalyst and preparation method thereof, the preparation of photocatalyst
Method is simple, easily operates, low cost, is applied to the process for chromate waste water, effective, repeatable utilization.
A kind of Fe3O4-C@Bi2O3The preparation method of-BiOI photocatalyst, comprises the steps:
(1) by FeCl3·6H2O is dissolved in ethylene glycol, is subsequently adding sodium acetate and Polyethylene Glycol, is stirred vigorously, obtains all
Even reddish brown color cloud liquid A;By Bi (NO3)3·5H2O dissolves in ethylene glycol and the mixed solvent of ethanol and stirs, formation solution B;
(2) reddish brown color cloud liquid A is instilled in solution B by stirring (magnetic agitation) simultaneously, the most ultrasonic, is shifted by mixed solution
In autoclave, hydro-thermal reaction;
(3), after being cooled to room temperature after hydro-thermal reaction terminates, stirring (rotates stirring) simultaneously and adds KI solution, and regulation pH (uses
HNO3), continue stirring;Magnetic Isolation, washing (by water and washing with alcohol repeatedly), obtain Fe3O4-C@Bi2O3-BiOI。
Stirring in step (2) uses stirring in magnetic agitation, step (3) to use and rotates stirring.
It is modified that the present invention carries out semiconductors coupling to bismuth oxide, by hydro-thermal method, is introduced by magnetic ferroferric oxide, it is possible to
The magnetic photocatalyst of high visible response is prepared in realization, and is applied to heavy metal-containing wastewater treatment field, has the highest
Using value.
The present invention uses a step hydrothermal synthesis method, it is achieved that Fe3O4And Bi2O3Preparation, and Fe3O4-C@Bi2O3Life
Become, and etched by acidity further, obtain Fe3O4-C@Bi2O3-BiOI magnetic photocatalyst.The photocatalysis of the present invention
Agent, is with Bi2O3Based on, prepare BiOI, the two forms hetero-junctions and catalyst band gap is reduced, it is seen that photoresponse substantially carries
High.Bi203Band-gap energy be 2.75eV, valence band polarization;The conduction band exciting rear BiOI compares Bi203Conduction band is lower, and on it, electronics is permissible
It is easy to be transferred to Bi203Conduction band, thus more reduce for chromium.Meanwhile, the valence band of BiOI is higher, Bi203Hole in valence band
Being transferred on BiOI, be more beneficial for the separation of electron-hole, improve light induced electron quantity, electronics is for being reduced to Cr (VI)
Cr (III), Hole oxidation water, water serves as sacrifice agent effect.Cr (VI) is reduced into Cr (III), and toxicity reduces, the Cr of formation
(III) can be easy to be removed by precipitation, thus reach the purpose of processing waste water containing chrome.
In the catalyst that the present invention prepares the most collaborative between each composition, with Fe3O4For kernel, prepare high-ratio surface
Long-pending Fe3O4@Bi2O3-BiOI, increase catalyst contacts with pollutant, is doped into the C of generation simultaneously, improves light induced electron
Transfer rate so that more electronics separates with hole, thus have more light induced electron to reduce for Cr (VI).The opposing party
Face, Fe3O4There is magnetic, the separation of catalyst, recovery can be realized well.Meanwhile, the Fe of black3O4With C and Bi2O3-BiOI
Collaborative, can further improve visible light-responded, so that catalyst has higher visible light activity.Fe3O4-C@Bi2O3-
BiOI is compared to Fe3O4@Bi2O3, it is seen that light absorbs to be increased at most, the most substantially occurs that ultra-violet (UV) band absorbs and reduces.Thus,
The Fe of modified preparation3O4-C@Bi2O3-BiOI can preferably utilize nature light, thus extensively apply for it and lay good basis.
Proportioning raw materials in the present invention, it is preferable that Bi (NO when reddish brown color cloud liquid A mixes with solution B3)3·5H2O with
FeCl3·6H2O mol ratio is 1~3:1, Polyethylene Glycol and Bi (NO3)3·5H2O mol ratio is 1:1~4;Further preferably, Bi
(NO3)3·5H2O and FeCl3·6H2O mol ratio is 2~3:1, Polyethylene Glycol and Bi (NO3)3·5H2O mol ratio is 1:1~3;
The photocatalyst treatment prepared under this optimum condition reaches more than 90% containing clearance during hexavalent chromium wastewater;Most preferably, Bi
(NO3)3·5H2O and FeCl3·6H2O mol ratio is 3:1, Polyethylene Glycol and Bi (NO3)3·5H2O mol ratio is 1:2.
Further, when step (1) prepares reddish brown color cloud liquid A, FeCl3·6H2O and sodium acetate mol ratio are 1:4~6.
More preferably 1:5.Sodium acetate provides weakly alkaline environment, in protection course of reaction, prevents FeCl3·6H2O becomes Fe3O3。
Its amount is very few, easily produces a small amount of Fe3O3, too much can cause the waste of reagent.
Preferably, described ethylene glycol with the volume ratio of ethylene glycol in the mixed solvent volume of ethanol with ethanol is: VEthylene glycol:
VEthanol=1:2.
It is further preferred that during preparation solution B, Bi (NO3)3·5H2O is to be dissolved in second in terms of 0.04~0.08mol/L by concentration
In the mixed solvent of glycol and ethanol.
Preferably, in step (3) addition of KI solution with Bi (NO3)3·5H2O Yu KI mol ratio is 1~3:1 meter;Enter
The photocatalyst treatment prepared under this optimum condition of one step preferably 2~3:1 reaches containing clearance during hexavalent chromium wastewater
More than 90%;Most preferably 2:1.
The KI amount added can directly influence the BiOI of generation and measure, and KI volume, i.e. by KI concentration-response, influence whether
The concentration of reactant, and then ratio between each composition can be had an impact;The addition of Polyethylene Glycol influences whether C in catalyst
Content, dispersibility when also can prepare catalyst produces certain impact;The dosage of iron chloride, i.e. bismuth nitrate and iron chloride
Mol ratio, influence whether Bi in catalyst system2O3And Fe3O4Relative amount, Fe3O4Increase and can increase catalyst magnetic
Property, but magnetic increase can make reaction time catalizer assemble, additionally, it may also reduce Bi2O3Ratio, and then can be to catalyst activity
Produce impact.
In preparation method of the present invention, the preferred compositions of raw material is:
Bi (NO when reddish brown color cloud liquid A mixes with solution B3)3·5H2O and FeCl3·6H2O mol ratio is 2~3:1, poly-second
Glycol and Bi (NO3)3·5H2O mol ratio is 1:1~3;When preparing reddish brown color cloud liquid A, FeCl3·6H2O and sodium acetate mol ratio
For 1:4~6;In step (3), the addition of KI solution is with Bi (NO3)3·5H2O Yu KI mol ratio is 2~3:1 meters.
Most preferably, Bi (NO when reddish brown color cloud liquid A mixes with solution B3)3·5H2O and FeCl3·6H2O mol ratio is 3:
1, Polyethylene Glycol and Bi (NO3)3·5H2O mol ratio is 1:2;When preparing reddish brown color cloud liquid A, FeCl3·6H2O and sodium acetate mole
Ratio is 1:5;In step (3), the addition of KI solution is with Bi (NO3)3·5H2O Yu KI mol ratio is 2:1 meter.
Hydro-thermal reaction time and temperature influence whether the material composition that catalyst generates, and catalyst pattern.Preferably,
Hydrothermal temperature 180~220 DEG C, time 8~12 hours, it is further preferred that temperature is 200 DEG C, 10 hours time.
Preferably, adding KI concentration is 0.1~0.3mol/L, more preferably 0.2mol/L.
The pH numerical value of regulation influences whether the generation of BiOI, and under acid condition, KI etches Bi2O3Speed is accelerated, and is conducive to
BiOI generates, and is also beneficial to the utilization of reactant.
Described step (3) regulation pH is 3~5 or uncomfortable, is 3~5 as preferably regulating pH, more preferably, regulation pH is
3.Use HNO3Carry out pH regulator.
Preferably, by water and washing with alcohol 3 times.
Preferably, 60 DEG C are vacuum dried 3 hours.
A kind of preparation method of the preparation method of the magnetic photocatalyst of the present invention, most preferred technique scheme is as follows:
(1) by FeCl3·6H2O is dissolved in ethylene glycol, forms settled solution, is subsequently adding sodium acetate and Polyethylene Glycol,
It is stirred vigorously 30min, obtains uniform reddish brown color cloud liquid A;By Bi (NO3)3·5H2O is dissolved in the mixed solvent of L ethylene glycol and ethanol
In (VEthylene glycol:VEthanol=1:2) and stir 40min, form solution B;
(2) under the conditions of magnetic agitation, reddish brown color cloud liquid A is instilled in solution B, take out magnetic stir bar, the most ultrasonic
40min, transfers to mixed solution in autoclave, 200 DEG C of hydro-thermal reactions 10 hours;
(3) after being cooled to room temperature, rotate stirring, add KI solution, use HNO3Regulation pH is 3, continues stirring.Magnetic is divided
From, by water and washing with alcohol 3 times, then 60 DEG C are vacuum dried 3 hours, obtain Fe3O4-C@Bi2O3-BiOI;
Wherein: Bi (NO when reddish brown color cloud liquid A mixes with solution B3)3·5H2O and FeCl3·6H2O mol ratio is 3:1, gathers
Ethylene glycol and Bi (NO3)3·5H2O mol ratio is 1:2;When preparing reddish brown color cloud liquid A, FeCl3·6H2O with sodium acetate mol ratio is
1:5;In step (3), the addition of KI solution is with Bi (NO3)3·5H2O Yu KI mol ratio is 2:1 meter.
The present invention also provides for the Fe that a kind of preparation method as described in claim 1~8 any claim prepares3O4-
C@Bi2O3-BiOI photocatalyst.
The present invention also provides for a kind of such as described Fe3O4-C@Bi2O3-BiOI photocatalyst answering in processing waste water containing chrome
With.
It is an object of the invention to provide a kind of Fe3O4-C@Bi2O3-BiOI photocatalyst and preparation method thereof, Bi2O3With
BiOI forms hetero-junctions, is aided with C, improves the absorption to light and promotes electron transfer, and introducing Fe3O4So that catalyst is with magnetic
Property, to realize recovery and the recycling of catalyst.Fe3O4-C@Bi2O3-BiOI photocatalyst is to the place containing Cr (VI) waste water
Reason, under the combination of above-mentioned each optimum condition, treatment effect is more preferable.
Beneficial effects of the present invention has:
(1) photocatalyst preparation method is simple, low cost;
(2) visible light-responded good, utilization rate is high;
(3) Cr (VI) being had the highest reducing power, reaction rate is fast.
Accompanying drawing explanation
Fig. 1 is the UV-vis-DRS comparison diagram of photocatalyst in the embodiment of the present invention 2.
Fig. 2 is four kinds of photocatalyst reduction Cr (VI) effect contrast figures in the embodiment of the present invention 3.
Fig. 3 is that in the embodiment of the present invention 4, different Polyethylene Glycol are with under bismuth nitrate molar ratio, and the photocatalyst of preparation is also
Former Cr (VI) effect contrast figure.
Fig. 4 is that in the embodiment of the present invention 5, different bismuth nitrate are with under iron chloride molar ratio, and the photocatalyst of preparation reduces
Cr (VI) effect contrast figure.
Fig. 5 be in the embodiment of the present invention 6 different bismuth nitrate with under KI molar ratio, the photocatalyst reduction Cr of preparation
(VI) effect contrast figure.
Fig. 6 be the embodiment of the present invention 7 is adjusted pH and is not adjusted pH under the conditions of, the UV-vis-DRS of the photocatalyst of preparation contrast
Figure.
Fig. 7 be the embodiment of the present invention 7 is adjusted pH and is not adjusted pH under the conditions of, the photocatalyst of preparation reduction Cr (VI) effect pair
Than figure.
Detailed description of the invention
In conjunction with Figure of description and specific embodiment, the present invention is further described.
Raw material used below is commercial goods.
Embodiment 1
One, Fe3O4@Bi2O3Preparation method:
(1) by 0.18 gram of FeCl3·6H2O is dissolved in 10mL ethylene glycol, forms settled solution, is subsequently adding 0.47g vinegar
Acid sodium and 2.6mL polyethylene glycol 200 solution, be stirred vigorously 30min, obtain uniform reddish brown color cloud liquid A;By the Bi (NO of 0.97g3)3·
5H2O is dissolved in (V in the ethylene glycol of 51mL and the mixed solvent of ethanolEthylene glycol:VEthanol=1:2) and stir 40min, form solution B;
(2) under the conditions of magnetic agitation, reddish brown color cloud liquid A is instilled in solution B, take out magnetic stir bar, the most ultrasonic
30min, transfers to mixed solution in autoclave, 200 DEG C of hydro-thermal reactions 10 hours;
(3), after being cooled to room temperature, Magnetic Isolation, by water and washing with alcohol 3 times, then 60 DEG C are vacuum dried 3 hours, obtain
Fe3O4@Bi2O3。
Two, Fe3O4-C@Bi2O3Preparation method:
(1) in 10mL ethylene glycol, add 0.47g sodium acetate and 2.6mL polyethylene glycol 200 solution, be stirred vigorously
30min, obtains uniform reddish brown color cloud liquid A;By the Bi (NO of 0.97g3)3·5H2O is dissolved in the ethylene glycol of 51mL and the mixing of ethanol
(V in solventEthylene glycol:VEthanol=1:2) and stir 40min, form solution B;
(2) under the conditions of magnetic agitation, reddish brown color cloud liquid A is instilled in solution B, take out magnetic stir bar, the most ultrasonic
30min, transfers to mixed solution in autoclave, 200 DEG C of hydro-thermal reactions 10 hours;
(3), after being cooled to room temperature, Magnetic Isolation, by water and washing with alcohol 3 times, then 60 DEG C are vacuum dried 3 hours, obtain
Fe3O4-C@Bi2O3。
Three, Fe3O4@Bi2O3-BiOI preparation method:
(1) by 0.18 gram of FeCl3·6H2O is dissolved in 10mL ethylene glycol, forms settled solution, is subsequently adding 0.47g vinegar
Acid sodium, is stirred vigorously 30min, obtains uniform reddish brown color cloud liquid A;By the Bi (NO of 0.97g3)3·5H2O is dissolved in the ethylene glycol of 51mL
With (V in the mixed solvent of ethanolEthylene glycol:VEthanol=1:2) and stir 40min, form solution B;
(2) under the conditions of magnetic agitation, reddish brown color cloud liquid A is instilled in solution B, take out magnetic stir bar, the most ultrasonic
30min, transfers to mixed solution in autoclave, 200 DEG C of hydro-thermal reactions 10 hours;
(3) after being cooled to room temperature, rotate stirring, add KI solution, use HNO3Regulation pH is 3, continues stirring.Magnetic is divided
From, by water and washing with alcohol 3 times, then 60 DEG C are vacuum dried 3 hours, obtain Fe3O4@Bi2O3-BiOI。
Four, Fe3O4-C@Bi2O3-BiOI preparation method:
(1) by 0.18 gram of FeCl3·6H2O is dissolved in 10mL ethylene glycol, forms settled solution, is subsequently adding 0.47g vinegar
Acid sodium and 2.6mL polyethylene glycol 200 solution, be stirred vigorously 30min, obtain uniform reddish brown color cloud liquid A;By the Bi (NO of 0.97g3)3·
5H2O is dissolved in (V in the ethylene glycol of 51mL and the mixed solvent of ethanolEthylene glycol:VEthanol=1:2) and stir 40min, form solution B;
(2) under the conditions of magnetic agitation, reddish brown color cloud liquid A is instilled in solution B, take out magnetic stir bar, the most ultrasonic
30min, transfers to mixed solution in autoclave, 200 DEG C of hydro-thermal reactions 10 hours;
(3) after being cooled to room temperature, rotate stirring, add KI solution, use HNO3Regulation pH is 3, continues stirring.Magnetic is divided
From, by water and washing with alcohol 3 times, then 60 DEG C are vacuum dried 3 hours, obtain Fe3O4-C@Bi2O3-BiOI。
Embodiment 2
Photocatalyst Fe prepared by embodiment 13O4@Bi2O3、Fe3O4-C@Bi2O3、Fe3O4-C@Bi2O3-BiOI carries out red
External spectrum scanning and UV-Vis DRS scan, and obtain UV-vis-DRS comparison diagram 1.
Such as Fig. 1, it can be seen that Fe3O4-C@Bi2O3、Fe3O4-C@Bi2O3Visible ray is had well by-BiOI
Response, Fe3O4@Bi203Modified, the absorption to the visible ray of 400-600nm is obviously enhanced.Fe3O4-C@Bi2O3-BiOI compares
In Fe3O4@Bi203, it is seen that light absorbs to be increased at most, the most substantially occurs that ultra-violet (UV) band absorbs and reduces.Thus, modified preparation
Fe3O4-C@Bi2O3-BiOI can be good at utilizing visible ray, thus significantly improves its visible light activity.
Embodiment 3
In 50mL chromate waste water (Cr (VI) concentration 80 μm ol/L), adding the photocatalyst of 50mg, uncomfortable pH, in dark place
30min is to adsorption equilibrium in stirring, opens visible light source, reacts 35min, and it is little by 100 that Cr (VI) is reduced to toxicity by light induced electron
Again, easily there is the Cr (III) of coordination precipitation.
Wherein photocatalyst uses the photocatalyst Fe of embodiment 1 preparation3O4@Bi2O3、Fe3O4-C@Bi2O3、Fe3O4@
Bi2O3-BiOI、Fe3O4-C@Bi2O3-BiOI, carries out reduction Cr (VI) Contrast on effect, result such as Fig. 2.
Under similarity condition, the Fe of modified preparation3O4-C@Bi2O3、Fe3O4@Bi2O3-BiOI、Fe3O4-C@Bi2O3-BiOI
The effect of reduction chromium all has and promotes in various degree, Cr (VI) rate of reduction: Fe3O4-C@Bi2O3-BiOI>Fe3O4@Bi2O3-BiOI>
Fe3O4-C@Bi2O3>Fe3O4@Bi2O3.In 35min, Fe3O4@Bi2O3Chromium percent reduction is 35.47%, Fe3O4-C@Bi2O3-
BiOI is 89.98% for the clearance of Cr (VI), about Fe3O4@Bi2O32.5 again.
Embodiment 4
The addition of Polyethylene Glycol influences whether the content of C in catalyst, also influences whether dispersion time prepared by catalyst
Property.Change Fe in embodiment 13O4-C@Bi2O3Polyethylene Glycol addition, i.e. Polyethylene Glycol and bismuth nitrate in-BiOI preparation method
Mol ratio, prepare catalyst series, and by the chromium restoring operation of embodiment 3, contrast, obtain Fig. 3.
Such as Fig. 3, along with the increase of Polyethylene Glycol Yu the mol ratio of bismuth nitrate, the removal rate of Cr (VI) is gradually increased, when
When the mol ratio of Polyethylene Glycol and bismuth nitrate is increased to 1:1 by 1:2, the percent reduction increasing degree of Cr (VI) is little.Comprehensive materials are examined
Considering, Polyethylene Glycol is optimum when being 1:2 with the mol ratio of bismuth nitrate.
Embodiment 5
The dosage of iron chloride, i.e. bismuth nitrate and the mol ratio of iron chloride, influence whether Bi in catalyst system2O3With
Fe3O4Relative amount, Fe3O4Increase and can increase catalyst magnetic, but magnetic increase can make reaction time catalizer assemble,
Additionally, it may also reduce Bi2O3Ratio, and then have influence on catalyst activity.Change Fe in embodiment 13O4-C@Bi2O3Prepared by-BiOI
In method, bismuth nitrate and the mol ratio of iron chloride, prepare catalyst series, and by the chromium restoring operation of embodiment 3, contrast,
Obtain Fig. 4.
When increasing to 3:1 such as the mol ratio of Fig. 4, bismuth nitrate and iron chloride when 2:1, catalyst activity increases little, this
Time catalyst magnetic higher.Thus, combination property and magnetic consider, bismuth nitrate is preferably chosen as 2:1 with the mol ratio of iron chloride.
Embodiment 6
Bismuth nitrate and the ratio of KI, the i.e. dosage of KI, can directly influence the BiOI amount of generation, and then affect each composition
Between ratio.Change Fe in embodiment 13O4-C@Bi2O3In-BiOI preparation method, bismuth nitrate and the mol ratio of the ratio of KI, make
Standby catalyst series, and by the chromium restoring operation of embodiment 3, contrast, obtain Fig. 5.
From figure, it can be seen that the ratio of bismuth nitrate and KI is when 1:1 becomes 2:1, and the reduction effect of Cr (VI) increases bright
Aobvious, and when being further increased to 3:1, the reduction efficiency of Cr (VI) increases inconspicuous.Thus, the ratio of bismuth nitrate and KI elects 2 as:
When 1, the most properly.
Embodiment 7
The pH numerical value of regulation influences whether the generation of BiOI, and under acid condition, KI etches Bi2O3Speed is accelerated, and is conducive to
BiOI generates, and is also beneficial to the utilization of reactant.Change Fe in embodiment 13O4-C@Bi2O3Regulation in-BiOI preparation method
PH numerical value, prepares catalyst series, and by the chromium restoring operation of embodiment 3, contrasts, obtain Fig. 7.
It addition, the sample adjusting pH to be 3 preparations is carried out ultraviolet-visible light diffuse-reflectance spectral scan, obtain UV-vis-DRS pair
Compare Fig. 6.
From fig. 6, it can be seen that adjusting pH is that the sample of 3 preparations is compared to not adjusting pH, it is seen that light absorbs to be increased, at 500-700nm
The absorption of the visible ray of wave band is remarkably reinforced, it is seen that photolytic activity should increased.
Found out by Fig. 7, pH numerical value is adjusted to acidity, be really conducive to the catalyst performance of preparation to improve, along with regulation
The reduction of pH numerical value, the reduction effect of Cr (VI) increases, and wherein, when pH is 3, effect is best.It is unfavorable to increase further due to acidity
In Fe3O4Stablize so that catalyst magnetic reduce, so pH numerical value is without reducing again.Thus, pH is preferable when being 3.