CN110090652A - A method of it preparing chlorine four and aoxidizes three bismuths/strontium ferrite composite magnetic catalysis material - Google Patents

A method of it preparing chlorine four and aoxidizes three bismuths/strontium ferrite composite magnetic catalysis material Download PDF

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CN110090652A
CN110090652A CN201910376329.0A CN201910376329A CN110090652A CN 110090652 A CN110090652 A CN 110090652A CN 201910376329 A CN201910376329 A CN 201910376329A CN 110090652 A CN110090652 A CN 110090652A
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srfe
strontium ferrite
catalysis material
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徐龙君
王海龙
刘成伦
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Chongqing University
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    • B01J35/00Catalysts, in general, characterised by their form or physical properties
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
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Abstract

A method of it preparing chlorine four and aoxidizes three bismuths/strontium ferrite composite magnetic catalysis material, belong to inorganic catalysis material technical field.The present invention is first prepared for retentive material strontium ferrite SrFe with hydro-thermal method12O19, then chlorine four has been prepared by hydro-thermal-roasting method and has aoxidized three bismuths/strontium ferrite Bi3O4Cl/SrFe12O19Composite magnetic catalysis material finally obtains magnetic photocatalytic material sample by dry and grinding.The method of the present invention preparation process is simple, few using equipment, low energy consumption.The Bi of preparation3O4Cl/SrFe12O19The magnetic property of composite magnetic catalysis material is stable, photocatalytic activity is high, under the irradiation of simulated solar irradiation xenon lamp, the rhodamine B solution for being 10mg/L with 0.1g composite magnetic catalysis material degradation 100mL concentration, illumination 60min reaches 97.3% to the degradation rate of rhodamine B, it is 92.4% to the magnetic rate of recovery of photochemical catalyst under externally-applied magnetic field, is 95.7% to the degradation rate of rhodamine B after reusing 3 times.The product that the present invention prepares can be widely used for photocatalysis degradation organic contaminant field.

Description

It is a kind of to prepare the oxidation three bismuths/strontium ferrite composite magnetic catalysis material of chlorine four Method
Technical field
The present invention relates to a kind of chlorine four for preparing to aoxidize three bismuths/strontium ferrite (Bi3O4Cl/SrFe12O19) composite magnetic light urges The method for changing material, belongs to inorganic catalysis material technical field.
Background technique
Chlorine four aoxidizes three bismuth (Bi3O4Cl) as novel nano-photocatalyst, belong to the conductor photocatalysis material of stratiform Material, due to its excellent electrical properties, suitable position of energy band and efficient photocatalytic activity, in degradable organic pollutant side Face has received widespread attention.Bi3O4For Cl as bismuth-based oxide, structure is by [Cl] sheath and is clipped between two [Cl] layers [Bi3O4] layer composition, this unique structure can guarantee the foundation of therein electrostatic field, to promote photo-generated carrier Separation and transport.Bi3O4The preparation method of Cl mainly has hydro-thermal method, coprecipitation and roasting method etc..Common photochemical catalyst exists Can be dispersed in liquid in reaction system, it is difficult to separation and recycling and reusing, thus constrain photochemical catalyst popularization and Using.Physiochemical mutagens and the recycling of catalyst may be implemented in composite magnetic catalysis material under the action of externally-applied magnetic field, The shortcomings that energy consumption is high, low efficiency to overcoming conventional filtration way of recycling.
Strontium ferrite (SrFe12O19) belong to magneto-plumbite type ferrite, it is hexaplanar, there is high saturation and magnetic intensity, height Magnetic conductivity, low-loss, steady performance.Therefore with SrFe12O19For the composite magnetic catalysis material of magnetic matrix preparation With stable magnetism, be conducive to the recycling and recycling of catalyst.Common SrFe12O19Preparation method includes that chemistry is total The precipitation method, molten-salt growth method, hydro-thermal method, microemulsion method, self-assembly method, self-propagating high-temperature synthesis and sol-gel method etc..
Currently, to Bi3O4The research of Cl, which is mainly concentrated in, improves its photocatalytic activity aspect, and studies and how to prepare Bi3O4The report of the composite magnetic photochemical catalyst of Cl is less.As in " Catalysis Communications " 2016 volume 76 " Synthesis of AgCl/Bi3O4Cl composite and its photocatalytic activity in RhB Degradation under visible light " (documents 1) prepares pure Bi using roasting method3O4Then Cl is used again Hydro-thermal method prepares AgCl/Bi3O4Cl composite photo-catalyst.The disadvantage of this method is that: (1) Bi3O4Cl is by making in advance The Bi got ready2O3High-temperature roasting 6h is made at 700 DEG C with BiOCl, and preparation process is complicated, energy consumption is high, at high cost;(2) it prepares Bi3O4Cl and compound AgCl/Bi3O4Cl catalytic activity is not high, and 60min is respectively 69.9% He to the degradation rate of rhodamine B 94.4%;(3) photochemical catalyst is difficult to realize recycling and reusing, and operating cost is higher, easily leads to secondary pollution.
For another example patent of invention " a kind of preparation method of the composite bismuth vanadium photocatalyst of strontium ferrite load " (publication number: CN103480384A) (documents 2) prepare strontium ferrite with roasting method, then using impregnation-calcination method prepare strontium ferrite/ Pucherite composite magnetic photochemical catalyst.The disadvantage of this method is that: (1) strontium ferrite be 800~1000 DEG C roast 2~ 4h is made, and energy consumption is high;(2) the photocatalysis stability of the composite magnetic photochemical catalyst of this method preparation is poor, and light after the recovery is urged Agent is reduced to 60% by 93% to the degradation rate of methylene blue in 5h.
Summary of the invention
The purpose of the present invention is be directed to Bi3O4Cl is difficult to the problem of recycling, and proposes a kind of Bi3O4Cl/SrFe12O19It is multiple The preparation method of magnetic photocatalyst is closed, preparation method is simple, at low cost.The Bi of preparation3O4Cl/SrFe12O19Composite magnetic light Catalyst photocatalysis efficiency with higher under simulated solar irradiation irradiation, and convenient for being divided from liquid-phase system by externally-applied magnetic field From and recycling, catalyst after the recovery photocatalytic activity still with higher.Both simple and efficient realizes resource again to this method It utilizes, in turn avoids the possible secondary pollution of catalyst.
Bi of the present invention3O4Cl/SrFe12O19The preparation method is as follows:
(1)SrFe12O19Preparation
SrFe is prepared using hydro-thermal method12O19, the FeCl of 2.1624g is weighed respectively3·6H2The SrCl of O and 0.2666g2· 6H2O adds 20mL distilled water in beaker, and sonic oscillation makes it dissolve to obtain mixed solution;Under magnetic agitation effect, To the certain density NaOH solution of mixed solution and dripping, the pH for adjusting solution is 10, continues to stir 10min;After stirring Solution is transferred in the reaction kettle of 100mL, is reacted at 200 DEG C for 24 hours, cooling after the reaction was completed, filter, respectively with distilled water and Dust technology washs 5 times, dries at 80 DEG C for 24 hours, and finally grinding obtains SrFe12O19
(2)Bi3O4Cl/SrFe12O19The preparation of composite magnetic catalysis material
Weigh the Bi (NO of 0.97g3)3·5H2O is added in the ethylene glycol of 20mL, and suspension A is obtained after ultrasonic 10min, The NaCl for weighing 0.039g is dissolved in the distilled water of 50mL, obtains solution B after stirring 5min;Under the action of mechanical stirring, Solution B is added dropwise in suspension A, continues to stir 10min after dripping, obtains suspension C;Weighing mass fraction is 15%~25% SrFe12O19It being added in suspension C, stirring is transferred to after ten minutes in the reaction kettle liner of 100mL, and 160 Hydro-thermal reaction 12h obtains Bi at DEG C3O4Cl/SrFe12O19The presoma of photochemical catalyst;Cooling at room temperature, suction filtration, is washed with distillation It washs 5 times, and dry 12h at 80 DEG C;It will be put into 100mL ceramic crucible after drying sample grinding, is placed in Muffle furnace, at 500 DEG C 2h is roasted, Bi is obtained3O4Cl/SrFe12O19Composite magnetic catalysis material.
The present invention by adopting the above technical scheme, mainly has the following effects:
(1) Bi of the method for the present invention preparation3O4Cl/SrFe12O19The photocatalysis with higher of composite magnetic photochemical catalyst is living Property, under the irradiation of simulated solar irradiation xenon lamp, 0.1g composite magnetic photochemical catalyst Bi3O4Cl/SrFe12O19Handling 100mL concentration is The rhodamine B solution of 10mg/L reaches 97.3% to the degradation rate of rhodamine B after illumination 60min and (prepares better than documents 1 AgCl/Bi3O4Cl composite photo-catalyst).
(2) Bi of the method for the present invention preparation3O4Cl/SrFe12O19Composite magnetic photochemical catalyst is under the action of an external magnetic field The degradation rate that the rate of recovery is up to after reusing 92.4%, and 3 times still reaches 95.7%.
(3) Bi of the method for the present invention preparation3O4Cl/SrFe12O19Composite magnetic photochemical catalyst, specific surface area 6.11m2/ G, preparation manipulation is simple, and required equipment is few, and low energy consumption.
Detailed description of the invention
Fig. 1 is Bi3O4Cl、SrFe12O19And Bi3O4Cl/SrFe12O19X ray diffracting spectrum (XRD).
Fig. 2 is Bi3O4Cl、SrFe12O19And Bi3O4Cl/SrFe12O19Scanning electron microscope (SEM) photograph (SEM).
Fig. 3 is SrFe12O19And Bi3O4Cl/SrFe12O19Magnetic hysteresis return line chart.
Specific embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
It is a kind of to prepare Bi3O4Cl/SrFe12O19The preparation of composite magnetic catalysis material, the specific steps are as follows:
(1)SrFe12O19Preparation
SrFe is prepared using hydro-thermal method12O19, the FeCl of 2.1624g is weighed respectively3·6H2The SrCl of O and 0.2666g2· 6H2O adds 20mL distilled water in beaker, and sonic oscillation makes it dissolve to obtain mixed solution;Under magnetic agitation effect, To the certain density NaOH solution of mixed solution and dripping, the pH for adjusting solution is 10, continues to stir 10min;After stirring Solution is transferred in the reaction kettle of 100mL, is reacted at 200 DEG C for 24 hours, cooling after the reaction was completed, filter, respectively with distilled water and Dust technology washs 5 times, dries at 80 DEG C, and finally grinding obtains SrFe12O19
(2)Bi3O4Cl/SrFe12O19The preparation of composite magnetic catalysis material
Weigh the Bi (NO of 0.97g3)3·5H2O is added in the ethylene glycol of 20mL, and suspension A is obtained after ultrasonic 10min, The NaCl for weighing 0.039g is dissolved in the distilled water of 50mL, obtains solution B after stirring 5min;Under the action of mechanical stirring, Solution B is added dropwise in suspension A, continues to stir 10min after dripping, obtains suspension C;Weighing mass fraction is 15% SrFe12O19It is added in suspension C, stirring is transferred to after ten minutes in the reaction kettle liner of 100mL, and 160 DEG C are lauched Thermal response 12h obtains Bi3O4Cl/SrFe12O19The presoma of photochemical catalyst;Cooling at room temperature, suction filtration, is washed with distilled water 5 times, And 12h is dried at 80 DEG C;It will be put into 100mL ceramic crucible after drying sample grinding, be placed in Muffle furnace, in 500 DEG C of roasting 2h, Obtain Bi3O4Cl/SrFe12O19Composite magnetic catalysis material.
Embodiment 2
It is a kind of to prepare Bi3O4Cl/SrFe12O19The preparation of composite magnetic catalysis material, the specific steps are as follows:
(1)SrFe12O19Preparation
With (1) in embodiment 1.
(2)Bi3O4Cl/SrFe12O19The preparation of composite magnetic catalysis material
Weigh the Bi (NO of 0.97g3)3·5H2O is added in the ethylene glycol of 20mL, and suspension A is obtained after ultrasonic 10min, The NaCl for weighing 0.039g is dissolved in the distilled water of 50mL, obtains solution B after stirring 5min;Under the action of mechanical stirring, Solution B is added dropwise in suspension A, continues to stir 10min after dripping, obtains suspension C;Weighing mass fraction is 20% SrFe12O19It is added in suspension C, stirring is transferred to after ten minutes in the reaction kettle liner of 100mL, and 160 DEG C are lauched Thermal response 12h obtains Bi3O4Cl/SrFe12O19The presoma of photochemical catalyst;Cooling at room temperature, suction filtration, is washed with distilled water 5 times, And 12h is dried at 80 DEG C;It will be put into 100mL ceramic crucible after drying sample grinding, be placed in Muffle furnace, in 500 DEG C of roasting 2h, Obtain Bi3O4Cl/SrFe12O19Composite magnetic catalysis material.
Embodiment 3
It is a kind of to prepare Bi3O4Cl/SrFe12O19The preparation of composite magnetic catalysis material, the specific steps are as follows:
(1)SrFe12O19Preparation
With (1) in embodiment 1.
(2)Bi3O4Cl/SrFe12O19The preparation of composite magnetic catalysis material
Weigh the Bi (NO of 0.97g3)3·5H2O is added in the ethylene glycol of 20mL, and suspension A is obtained after ultrasonic 10min, The NaCl for weighing 0.039g is dissolved in the distilled water of 50mL, obtains solution B after stirring 5min;Under the action of mechanical stirring, Solution B is added dropwise in suspension A, continues to stir 10min after dripping, obtains suspension C;Weighing mass fraction is 25% SrFe12O19It is added in suspension C, stirring is transferred to after ten minutes in the reaction kettle liner of 100mL, and 160 DEG C are lauched Thermal response 12h obtains Bi3O4Cl/SrFe12O19The presoma of photochemical catalyst;Cooling at room temperature, suction filtration, is washed with distilled water 5 times, And 12h is dried at 80 DEG C;It will be put into 100mL ceramic crucible after drying sample grinding, be placed in Muffle furnace, in 500 DEG C of roasting 2h, Obtain Bi3O4Cl/SrFe12O19Composite magnetic catalysis material.
Experimental result
Bi prepared by embodiment 23O4Cl/SrFe12O19Catalytic degradation activity of the composite magnetic catalysis material to rhodamine B Most preferably.In order to facilitate comparison, it is prepared for Bi3O4Cl sample.Bi3O4Cl preparation method is to be added without in 2 step of embodiment (2) SrFe12O19
Bi3O4Shown in the XRD spectrum of Cl such as Fig. 1 (a), all diffraction maximums energy index turns to the Bi of monoclinic system in figure3O4Cl (JCPDS No.:36-0760), shows successfully to prepare Bi3O4Cl crystal;SrFe12O19XRD spectrum such as Fig. 1 (b) shown in, figure In all diffraction maximums can index turn to the SrFe of hexagon12O19(JCPDS No.:33-1340) shows successfully to prepare SrFe12O19Crystal;Bi3O4Cl/SrFe12O19XRD spectrum such as Fig. 1 (c) shown in, with pure Bi3O4The XRD spectrum of Cl compares hair It is existing, Bi3O4Cl/SrFe12O19Main diffraction peak and Bi3O4Cl is almost the same, but the diffraction maximum hair at 28.78 ° and 29.13 ° Raw obvious decrease, shows SrFe12O19It is compound to Bi3O4The preference direction of growth and crystal structure of Cl crystal have certain shadow It rings;There is SrFe at 33.15 ° simultaneously12O19Diffraction maximum, shows and SrFe12O19With Bi3O4Cl success is compound.
Bi3O4The SEM figure of Cl is as shown in Fig. 2 (a), it can be seen that Bi3O4Cl is made of nanometer sheet in irregular shape, is not had There is other impurities appearance;SrFe12O19SEM figure as shown in Fig. 2 (b), it can be seen that SrFe12O19For hexagon sheet, without it He occurs impurity;Bi3O4Cl/SrFe12O19SEM figure as shown in Fig. 2 (c), it can be seen that prepared Bi3O4Cl nanometer sheet is not Regularly it is supported on SrFe12O19On hexagon lamella, show successfully to prepare Bi3O4Cl/SrFe12O19Composite magnetic photocatalysis Agent.
SrFe12O19Magnetic parameter such as Fig. 3 (a) shown in, saturation magnetization 32.03emu/g, coercivity is 941.24Oe shows that material is retentive material;Bi3O4Cl/SrFe12O19Magnetic parameter such as Fig. 3 (b) shown in, be saturated magnetic Change intensity is 6.12emu/g, and coercivity 870.26Oe shows composite photo-catalyst Bi3O4Cl/SrFe12O19With stronger It is magnetic.
Photocatalysis experiment shows in the case where simulated solar irradiation xenon lamp irradiates, with 0.1g composite magnetic photocatalyst for degrading 100mL Concentration is the rhodamine B solution of 10mg/L, and illumination 60min reaches 97.3% to the degradation rate of rhodamine B, right under externally-applied magnetic field The magnetic rate of recovery of photochemical catalyst is 92.4%, and the degradation rate after reusing 3 times is 95.7%, is illustrated using prepared by the present invention Bi3O4Cl/SrFe12O19Composite magnetic photochemical catalyst photocatalytic activity with higher and stability.

Claims (2)

1. it is a kind of prepare chlorine four aoxidize three bismuths/strontium ferrite composite magnetic catalysis material method, it is characterised in that including with Lower step:
(1) preparation of strontium ferrite
SrFe is prepared using hydro-thermal method12O19, the FeCl of 2.1624g is weighed respectively3·6H2The SrCl of O and 0.2666g2·6H2O is total With being dissolved in 20ml distilled water, sonic oscillation makes it dissolve to obtain mixed solution;It is molten to mixing under the action of magnetic agitation Certain density NaOH is added dropwise in liquid, the pH for adjusting solution is 10, continues to stir 10min;Solution after stirring is transferred to It in the reaction kettle of 100mL, is reacted at 200 DEG C for 24 hours, cooling after the reaction was completed, suction filtration is washed with distilled water and dust technology respectively It 5 times, is dried at 80 DEG C for 24 hours, finally grinding obtains strontium ferrite SrFe12O19
(2) chlorine four aoxidizes the preparation of three bismuths/strontium ferrite composite magnetic catalysis material
Weigh the Bi (NO of 0.97g3)3·5H2O is added in the ethylene glycol of 20mL, and suspension A is obtained after ultrasonic 10min, is weighed The NaCl of 0.039g is dissolved in the distilled water of 50mL, obtains solution B after stirring 5min;By solution under the action of mechanical stirring B is added dropwise in suspension A, is continued to stir 10min after dripping, is obtained suspension C;Weigh mass fraction be 15%~ 25% SrFe12O19It is added in suspension C, stirring is transferred to after ten minutes in the reaction kettle liner of 100mL, and 160 DEG C are lauched Thermal response 12h obtains Bi3O4Cl/SrFe12O19The presoma of photochemical catalyst;Cooling at room temperature, suction filtration, is washed with distilled water 5 times, And 12h is dried at 80 DEG C;It will be put into 100mL ceramic crucible after drying sample grinding, be placed in Muffle furnace, in 500 DEG C of roasting 2h, It obtains chlorine four and aoxidizes three bismuths/strontium ferrite Bi3O4Cl/SrFe12O19Composite magnetic catalysis material.
2. chlorine four according to claim 1 aoxidizes three bismuths/strontium ferrite composite magnetic catalysis material preparation method, It is characterized in that realizing magnetic matrix strontium ferrite with hydro-thermal-roasting method preparation with active component chlorine four and aoxidizing the effective of three bismuths It is compound.
CN201910376329.0A 2019-05-07 2019-05-07 A method of it preparing chlorine four and aoxidizes three bismuths/strontium ferrite composite magnetic catalysis material Pending CN110090652A (en)

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殷秉歆: ""铋系可见光响应纳米材料的合成及其光催化降解抗生素性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN111151258A (en) * 2020-01-16 2020-05-15 重庆三峡学院 Carbon quantum dot modified n-n type MFe12O19/CeO2Preparation method of magnetic separation photocatalyst
CN111701605A (en) * 2020-06-29 2020-09-25 重庆大学 Method for preparing magnetic iodine hepta-bismuth oxide composite photocatalytic material
CN111744504A (en) * 2020-07-02 2020-10-09 重庆大学 Method for preparing magnetic chlorine-bismuth tetroxide composite photocatalyst
CN111974424A (en) * 2020-07-09 2020-11-24 重庆大学 Method for preparing magnetic dibromo-bismuth pentoxide composite photocatalytic material
CN112604647A (en) * 2020-12-14 2021-04-06 重庆大学 Preparation method of red mud-based strontium magnetic NaP zeolite adsorption material
CN114602518A (en) * 2022-04-14 2022-06-10 六盘水师范学院 Self-assembled three-dimensional BiOI/BaFe12O19Magnetic photocatalyst and preparation method and application thereof
CN114939416A (en) * 2022-07-01 2022-08-26 重庆大学 Preparation method of visible-light-responsive composite magnetic tin dioxide photocatalyst
CN114939416B (en) * 2022-07-01 2023-08-22 重庆大学 Preparation method of visible light response composite magnetic tin dioxide photocatalyst

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