CN109806889A - A kind of molybdenum disulfide/ferroferric oxide magnetic nano composite material and preparation method and application - Google Patents
A kind of molybdenum disulfide/ferroferric oxide magnetic nano composite material and preparation method and application Download PDFInfo
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Abstract
The present invention relates to magnetic nanometer composite material technical fields, and in particular to a kind of molybdenum disulfide/ferroferric oxide magnetic nano composite material and preparation method and application.The present invention provides a kind of molybdenum disulfide/ferroferric oxide magnetic nano composite materials, are flower type structure, combine to obtain including molybdenum disulfide and the ferroso-ferric oxide for being supported on molybdenum disulfide surface；Hetero-junctions is formed between the molybdenum disulfide and ferroso-ferric oxide.Molybdenum disulfide provided by the invention/ferroferric oxide magnetic nano composite material is for organic pollutant to the photocatalytic activity of TC relative to MoS2And Fe3O4172.8% and 71.3% has been respectively increased in material；And after recycling 5 times, 3.5% reduced by only to the photodegradation rate of TC.Test result shows that molybdenum disulfide provided by the invention/ferroferric oxide magnetic nano composite material is excellent for the photocatalytic degradation effect of organic pollutant and good cycling stability.
Description
Technical field
The present invention relates to magnetic nanometer composite material technical fields, and in particular to a kind of molybdenum disulfide/ferroso-ferric oxide magnetic
Property nanocomposite and its preparation method and application.
Background technique
Quadracycline is common antibiotic, and the antibiotic in the whole world annual at least 50% is used for animal husbandry and aquatic products
Aquaculture cannot be discharged into environment in the form of metabolin by the antibiotic that human body or animal fully absorb.Isopropanol and three
Ethanol amine is important chemical products and raw material, is widely used in pharmacy, cosmetics, plastics, fragrance, coating etc., belongs to the world
The 3rd class carcinogenic substance that health organization international cancer research institution announces.Tetramethyl piperidine is in chemistry, biology, food industry, agriculture
There is relatively broad application in the fields such as industry.These organic matters can all adversely affect the health of the mankind, so as to cause following
Environmental pollution dye.Therefore, people propose urgent requirement to the method for these organic pollutants of degrading.
Chinese patent CN104529048A discloses a kind of system and method for handling hardly degraded organic substance, by using
The coupling depth treatment process and precoated shet ultrafiltration membrane/reverse osmosis process of " catalytic ozonation technology+composite biotechnology "
Combination, realizing has preferably fracture and degradation to macromolecular substances difficult to degrade, effectively removes conventional depth processing work
Skill is difficult to the organic pollutant degraded.But its degradation technique is very complicated, it is at high cost.
Chinese patent CN105502775A discloses a kind of antibiotic waste water degradation technique, including addition persulfate, tune
PH value, first time ultraviolet irradiation, addition thiosulfate and second ultraviolet irradiation and etc., the technique can be in waste water
Antibiotic degrade, but its degradation technique is very complicated, at high cost.
Chinese patent CN108187669A discloses a kind of preparation method for tetracycline photocatalysis nano material of degrading
With application, the Ag-SrTiO of preparation3Nano material is 79.63% to the degradation rate of tetracycline in Xenon light shining 120min,
But its preparation cost is high, it is low to the degradation rate of tetracycline.
Molybdenum disulfide (MoS2) it is used as a kind of N-type semiconductor, with the layer structure of its peculiar " sandwich " in light
The fields such as catalysis, electrochemistry, sensor, supercapacitor and drug release have a wide range of applications.But MoS2Material morphology
Have a significant impact for its photocatalytic degradation, such as bulk MoS2Photo-catalysis capability compared with stratiform MoS2Photo-catalysis capability it is weak.And
And single MoS2In practical applications due to the problems such as there is easy to reunite, specific surface area is small, lamella is thicker, Chang Yin is led material
The problems such as electrical property is bad, and ion deinsertion process volume change is big, causes the recycling performance of material poor, to organic pollutant
Photo-catalysis capability is weak.
Summary of the invention
The purpose of the present invention is to provide a kind of molybdenum disulfide/ferroferric oxide magnetic nano composite material and its preparation sides
Method and application.Molybdenum disulfide provided by the invention/photocatalysis of the ferroferric oxide magnetic nano composite material to organic pollutant
Degradation rate is fast, degradation rate is high and cyclic utilization rate is high, stability is good.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of molybdenum disulfide/ferroferric oxide magnetic nano composite materials, which is characterized in that is flower pattern
Structure combines to obtain including molybdenum disulfide and the ferroso-ferric oxide for being supported on molybdenum disulfide surface；The molybdenum disulfide and four oxygen
Change and forms hetero-junctions between three-iron.
Preferably, in the molybdenum disulfide/ferroferric oxide magnetic nano composite material ferroso-ferric oxide mass fraction
It is 10~60%.
The present invention provides the preparations of molybdenum disulfide described in above-mentioned technical proposal/ferroferric oxide magnetic nano composite material
Method, comprising the following steps:
L-cysteine solution, sodium molybdate solution and ferroferric oxide nano granules dispersion liquid are mixed, hydro-thermal conjunction is carried out
At reaction, molybdenum disulfide/ferroferric oxide magnetic nano composite material is obtained.
Preferably, the concentration of the L-cysteine solution is 0.01~0.03mol/L；The concentration of the sodium molybdate solution
For 0.01~0.03mol/L；The concentration of the ferroferric oxide nano granules dispersion liquid is 8~12mg/L.
Preferably, the volume of the L-cysteine solution, sodium molybdate solution and ferroferric oxide nano granules dispersion liquid
Than for 1:(0.8~1.2): (0.05~0.8).
Preferably, in the ferroferric oxide nano granules dispersion liquid ferriferrous oxide particles granularity be 150~
200nm。
Preferably, the reaction temperature of the hydrothermal synthesis reaction is 150~200 DEG C, and the reaction time is 12~36h.
Preferably, the mixed mode is that sodium molybdate solution is added drop-wise in L-cysteine solution to mix, so
Ferroferric oxide nano granules dispersion liquid is added in gained mixed system afterwards.
Preferably, the speed of the dropwise addition is 7~20 drops/minute.
The present invention also provides molybdenum disulfide described in above-mentioned technical proposal/ferroferric oxide magnetic nano composite material or
The molybdenum disulfide that preparation method described in above-mentioned technical proposal obtains/ferroferric oxide magnetic nano composite material is in photocatalytic degradation
Application in organic pollutant.
The present invention provides a kind of molybdenum disulfide/ferroferric oxide magnetic nano composite materials, for flower type structure, including two
Molybdenum sulfide and the ferroso-ferric oxide for being supported on molybdenum disulfide surface combine to obtain；Shape between the molybdenum disulfide and ferroso-ferric oxide
At hetero-junctions.Molybdenum disulfide provided by the invention/ferroferric oxide magnetic nano composite material have flower type structure, the four of addition
Fe 3 O prevents the compound of molybdenum disulfide quantity of photogenerated charge carrier, a series of as the electron capture center of photoinduction
Active specy is produced in reaction process, is urged to enhance molybdenum disulfide/ferroferric oxide magnetic nano composite material light
Change activity, for photocatalysis degradation organic contaminant excellent effect, as shown in application examples of the present invention, curing provided by the invention
Molybdenum/ferroferric oxide magnetic nano composite material is to the photodegradation rate of TC relative to single MoS2Material improves 172.8%,
Relative to single Fe3O4Material improves 71.3%；And after recycling 5 times, to the photodegradation rate of TC still 96% with
On, 3.5% is merely reduced, shows molybdenum disulfide provided by the invention/ferroferric oxide magnetic nano composite material for having
The photocatalysis effect of machine pollutant is excellent and good cycling stability.
The present invention provides the preparations of molybdenum disulfide described in above-mentioned technical proposal/ferroferric oxide magnetic nano composite material
Method, comprising the following steps: L-cysteine solution, sodium molybdate solution and ferroferric oxide nano granules dispersion liquid are mixed,
Hydrothermal synthesis reaction is carried out, molybdenum disulfide/ferroferric oxide magnetic nano composite material is obtained.Preparation method provided by the invention
High income, purity is high, as shown in the Examples, yield are 90.5~92.6%, and purity is 93.5~95.2%, and reaction condition
Mildly, easy to operate, energy consumption it is low, be suitable for industrialized production.
Detailed description of the invention
Fig. 1 is light degradation mechanism figure of the molybdenum disulfide/ferroferric oxide magnetic nano composite material to TC；
Fig. 2 is MoS2/Fe3O4The x-ray diffraction pattern of magnetic nanometer composite material；
Fig. 3 is molybdenum disulfide/ferroferric oxide magnetic nano composite material scanning electron microscope (SEM) photograph；
Fig. 4 is MoS2、Fe3O4And MoS2/Fe3O4Photocatalytic degradation efficiency of (25wt%) magnetic nanometer composite material to TC
Effect picture；
Fig. 5 is MoS2、Fe3O4、MoS2/Fe3O4(12.5wt%), MoS2/Fe3O4(25wt%), MoS2/Fe3O4
(37.5wt%) and MoS2/Fe3O4Photocatalytic degradation efficiency effect picture of (50wt%) magnetic nanometer composite material to TC；
Fig. 6 is MoS2/Fe3O4Cyclical stability effect of (25wt%) magnetic nanometer composite material to TC photocatalytic degradation
Figure.
Specific embodiment
The present invention provides a kind of molybdenum disulfide/ferroferric oxide magnetic nano composite materials, for flower type structure, including two
Molybdenum sulfide and the ferroso-ferric oxide for being supported on molybdenum disulfide surface combine to obtain；Shape between the molybdenum disulfide and ferroso-ferric oxide
At hetero-junctions.
In the present invention, in the molybdenum disulfide/ferroferric oxide magnetic nano composite material ferroso-ferric oxide quality
Score is preferably 10~60%, and more preferably 12.5~50%, most preferably 20~40%.The present invention passes through control curing
The mass fraction of ferroso-ferric oxide in molybdenum/ferroferric oxide magnetic nano composite material, due to Fe3O4Addition, as photoinduction
Electron capture center, prevent the compound of molybdenum disulfide quantity of photogenerated charge carrier, active specy generated in series reaction,
Enhance photocatalytic activity, so as to greatly improve the molybdenum disulfide/ferroferric oxide magnetic nano composite material for having
The photocatalysis performance of machine pollutant；Fe in composite material3O4Mass fraction it is excessive, will cause to MoS2Covering surface it is excessive, from
And reduce N-type semiconductor MoS2Photocatalysis performance；Fe3O4Mass fraction it is too small, the quantity of photogenerated charge current-carrying of molybdenum disulfide can be made
Son generation is most of compound, to reduce the photocatalytic activity of composite material.
In the present invention, the molybdenum disulfide/ferroferric oxide magnetic nano composite material specific surface area is preferably 15
~25m2/g；The molybdenum disulfide/ferroferric oxide magnetic nano composite material granularity is preferably 150~200nm.
Molybdenum disulfide provided by the invention/ferroferric oxide magnetic nano composite material is flower type structure, including curing
Molybdenum and the ferroso-ferric oxide for being supported on molybdenum disulfide surface combine to obtain；It is formed between the molybdenum disulfide and ferroso-ferric oxide different
Matter knot.Molybdenum disulfide provided by the invention/ferroferric oxide magnetic nano composite material is relative to single molybdenum disulfide or four
For Fe 3 O material, photocatalysis performance is significantly improved.
The present invention provides the preparations of molybdenum disulfide described in above-mentioned technical proposal/ferroferric oxide magnetic nano composite material
Method, comprising the following steps:
L-cysteine solution, sodium molybdate solution and ferroferric oxide nano granules dispersion liquid are mixed, hydro-thermal conjunction is carried out
At reaction, molybdenum disulfide/ferroferric oxide magnetic nano composite material is obtained.
In the present invention, the concentration of the L-cysteine solution is preferably 0.01~0.03mol/L, more preferably
0.015~0.025mol/L, most preferably 0.02mol/L.In the present invention, the concentration of the sodium molybdate solution is preferably 0.01
~0.03mol/L, more preferably 0.01~0.025mol/L, most preferably 0.01~0.02mol/L.In the present invention, described
The concentration of ferroferric oxide nano granules dispersion liquid is preferably 8~12mg/L, more preferably 9~11mg/L, most preferably 10mg/
L.In the present invention, the volume ratio of the L-cysteine solution, sodium molybdate solution and ferroferric oxide nano granules dispersion liquid
Preferably 1:(0.8~1.2): (0.05~0.8), more preferably 1:(0.9~1.1): (0.2~0.8), most preferably 1:1:
0.4。
In the present invention, the preparation method of the ferroferric oxide nano granules dispersion liquid is preferably by Fe3O4Particle and super
Pure water mixing, then carries out ultrasonic disperse for gained mixed liquor, obtains ferroferric oxide nano granules dispersion liquid.In the present invention
In, the temperature of the ultrasonic disperse is preferably 20~30 DEG C, and more preferably 24~26 DEG C；The time of the ultrasonic disperse is preferably
25~35min, more preferably 30min.In the present invention, ferroso-ferric oxide in the ferroferric oxide nano granules dispersion liquid
The granularity of grain is preferably 150~200nm, and the granularity of more preferably 180~200nm, ferriferrous oxide particles are excessive or too small, no
It only will affect MoS2/Fe3O4The yield and purity of magnetic nanometer composite material, and the photocatalysis performance of composite material can be reduced.
In the present invention, sodium molybdate solution is preferably added drop-wise in L-cysteine solution and carries out by the mixed mode
Then ferroso-ferric oxide solution is added in mixing in gained mixed system.In the present invention, sodium molybdate solution is added drop-wise to L- half
It is mixed in cystine solution, obtains molybdenum disulfide；The dropwise addition carries out under agitation, and the speed of the stirring is preferred
For 400~600r/min, more preferably 450~550r/min, most preferably 550r/min；The temperature of the stirring is preferably 20
~30 DEG C, more preferably 22~28 DEG C, most preferably 25 DEG C.In the present invention, the speed of the dropwise addition be preferably 7~20 drop/
Minute, more preferably 10~20 drops/minute；Rate of addition is too fast, will lead to the MoS of generation2Granularity is bigger than normal, rate of addition mistake
Slowly, it will lead to the MoS of generation2Granularity is less than normal.Pass through the order of addition and ferroso-ferric oxide solution for controlling raw material in the present invention
Rate of addition can control MoS generated2Granularity is 150~200nm, it is made to be not easy to sink in photocatalytic degradation experiment greatly
Drop, is uniformly dispersed, is easily isolated after experiment, to improve MoS2/Fe3O4The yield and purity of magnetic nanometer composite material, and
Be conducive to improve the photocatalysis performance of composite material.
In the present invention, it is described in gained mixed system be added ferroso-ferric oxide solution preferably under stirring conditions into
Row, the time of the stirring is preferably 30~90min, more preferably 40~80min, most preferably 50~60min；The stirring
Temperature and revolving speed with preferably and sodium molybdate solution be added drop-wise in L-cysteine solution stirred in mixed process
Temperature is identical with revolving speed.
In the present invention, the reaction temperature of the hydrothermal synthesis reaction is preferably 150~200 DEG C, more preferably 170~
190 DEG C, most preferably 180 DEG C；The reaction time of the hydrothermal synthesis is preferably 12~36h, more preferably 20~36h, optimal
It is selected as 24 hours.The present invention by control hydrothermal synthesis reaction reaction temperature and the time, advantageously form stable molybdenum disulfide/
Ferroferric oxide magnetic nano composite material.
It in the present invention, further include that solid-liquid point is carried out to system obtained by hydrothermal synthesis after the completion of the hydrothermal synthesis reaction
From, washing and dry.In the present invention, the mode of the separation of solid and liquid is preferably centrifuged, and the revolving speed of the centrifugation is preferably
5000~9000r/min, more preferably 7000~8000r/min；The time of the centrifugation is preferably 5~10min, more preferably
8~10min.In the present invention, the washing is preferably alternately washed using pure water and dehydrated alcohol；The number of the washing is preferred
It is 4~6 times, more preferably 4 times.The present invention is not particularly limited the drying, using drying mode well known in the art
, preferably gained system is dissolved in dehydrated alcohol and being dried.
The present invention also provides molybdenum disulfide described in above-mentioned technical proposal/ferroferric oxide magnetic nano composite material or
The molybdenum disulfide that preparation method described in above-mentioned technical proposal obtains/ferroferric oxide magnetic nano composite material is in photocatalytic degradation
Application in organic pollutant.In the present invention, the organic pollutant preferably includes quadracycline (TC).
In the present invention, the light degradation of the quadracycline (TC), specifically, being by MoS2/Fe3O4Magnetic Nano is multiple
Condensation material and water mixing, carry out ultrasonic disperse；It is placed in photochemical reaction instrument, is stirred under the premise of not opening xenon source
It mixes, to ensure that the adsorption-desorption of TC and photocatalyst surface reach balance；Then hydrogen peroxide is added into reaction vessel, opens
Light source carries out photocatalytic degradation reaction, and gained system is separated by solid-liquid separation, and measures gained supernatant using ultraviolet specrophotometer
The concentration of TC in liquid；The photocatalytic degradation efficiency calculation formula of TC is as follows:
The photocatalytic degradation efficiency of TC=(1-Ct/Co) × 100%,
In formula, C0For the initial concentration 30mg/L of TC；CtFor the concentration of TC in different moments supernatant to be measured.
In the present invention, in order to verify molybdenum disulfide/ferroferric oxide magnetic nano composite material to the light degradation machine of TC
Reason, i.e. lightwave CATV-like reaction mechanism, have carried out free radical under hydrogen peroxide existence condition and electron hole capture is tested,
As shown in Figure 1.After adding IPA, the degradation rate of TC drops to 31.02%, illustrates that OH has apparent effect to TC degradation.With
IPA is compared, and TEOA and 4-hydroxy-TEMPO is added in light-catalyzed reaction system, and degradation rate is declined slightly.Therefore, MoS2/
Fe3O4The photocatalytic activity of magnetic nanometer composite material significantly improves, the reason is that H in hydrogen peroxide2O2Elimination or activity point
Solution, the i.e. generation of activity OH free radical, it is determined that OH free radical plays a major role in embryonic stem-like cells.It reacts machine
It manages as follows:
MoS2/Fe3O4+hυ→e-+h+ (1)
Fe3++e-→Fe2+ (2)
H2O2+Fe2+→Fe3++·OH+OH- (3)
OH+TC=H2O+CO2 (4)
The present invention has successfully prepared the molybdenum disulfide with strong photocatalytic activity/tetra- oxidations three using simple method
Ferromagnetic nano composite material；It, which is applied to photocatalytic degradation TC, has excellent photocatalytic activity, in H2O2Under the conditions of existing
For TC removal rate in radiation of visible light 40min almost up to 100%, rate of photocatalytic oxidation is fast, and degradation rate is high；In conjunction with it
Stability inquiry experiment it is found that molybdenum disulfide/ferroferric oxide magnetic nano composite material cyclic utilization rate is high, stability is good,
It repeatedly uses rear photocatalysis effect to lower less than 4%, have and its important practical application value.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
Low whipping speed be 500r/min under conditions of, by 10mL concentration be 0.01mol/L sodium molybdate solution with 15 drop/
The speed of minute is at the uniform velocity added drop-wise in the L-cysteine solution that 10mL concentration is 0.01mol/L, is continued to stir 30min, be obtained
Mixed solution；
The Fe for being 200nm by 10mg granularity3O4Particle and the mixing of 1L ultrapure water, carry out ultrasound under the conditions of temperature is 25 DEG C
Disperse 30min, obtains the ferroferric oxide nano granules dispersion liquid that concentration is 10mg/L；
Ferroferric oxide nano granules dispersion liquid described in 2mL and the mixed solution are added in reaction kettle, stirred
80min, then under the conditions of 180 DEG C carry out hydrothermal synthesis reaction for 24 hours, then by gained system under the conditions of 8000r/min from
Obtained solid material is alternately washed 4 times altogether using pure water and dehydrated alcohol, is then dissolved in dehydrated alcohol and dries by heart 10min,
Obtain Fe3O4Content is the MoS of 12.5wt%2/Fe3O4Magnetic nanometer composite material is labeled as MoS2/Fe3O4(12.5wt%)；
Its specific surface area is 22.5m2/ g, granularity 200nm, yield 90.5%, purity 95.2%.
MoS2/Fe3O4Magnetic nanometer composite material, Fe3O4And MoS2X-ray diffraction spectra it is as shown in Figure 2.It can from Fig. 2
Know, pure Fe3O4Peak type be 6 typical peaks, be located at 30.1 °, 35.5 °, 43.1 °, 53.4 °, 57.0 ° and 62.6 °, can be right respectively
Answer a cube Fe3O4{ 220 }, { 311 }, { 400 }, { 422 }, { 511 } and { 440 } crystal face (JCPDS17-0320)；Pure MoS2Only occur
3 characteristic peaks 32.7 ° { 100 }, at 39.5 ° { 103 } and 58.3 ° { 110 }, can belong to respectively in about 2 θ=14.4 ° { 002 }
MoS2Hexagonal phase database (JCPDS37-1492).MoS prepared by the present invention2/Fe3O4The X- of magnetic nanometer composite material is penetrated
Line diffraction has characteristic peak: 2 θ=14.4 ° { 002 }, 30.1 ° { 220 }, 32.7 ° { 100 }, 35.5 ° at following 2 θ of the angle of diffraction
{ 311 }, 39.5 ° { 103 }, 43.1 ° { 400 }, 53.4 ° { 422 }, 57.0 ° { 511 } and 62.6 ° { 511 }.With pure Fe3O4And MoS2
It compares, MoS prepared by the present invention2/Fe3O4MoS in the X-ray diffraction spectrum of magnetic nanometer composite material2Characteristic peak it is more a height of excellent
Potential hump, due to a small amount of Fe3O4The presence of (12.5wt%), opposite MoS2For Fe3O4Diffracted intensity it is lower, and without other with
The relevant diffraction maximum of impurity, this shows to be successfully prepared MoS2/Fe3O4Composite material, MoS2And Fe3O4It combines closely, forms
MoS with high light catalytic activity2/Fe3O4Magnetic nanometer composite material.
MoS2/Fe3O4The scanning electron microscope (SEM) photograph of magnetic nanometer composite material is prepared by the present invention as shown in figure 3, as can be seen from Figure 3
MoS2/Fe3O4Magnetic nanometer composite material is flower type structure.
Embodiment 2
It is prepared according to the preparation method of embodiment 1, difference from example 1 is that, ferriferrous oxide nano
The amount that particle dispersion is added is 4mL, obtains Fe3O4Content is the MoS of 25wt%2/Fe3O4Magnetic nanometer composite material, label
For MoS2/Fe3O4(25wt%), specific surface area 16.8m2/ g, granularity 185nm, yield 90.6%, purity are
94.5%.
Embodiment 3
It is prepared according to the preparation method of embodiment 1, difference from example 1 is that, ferriferrous oxide nano
The amount that particle dispersion is added is 6mL, obtains Fe3O4Content is the MoS of 37.5wt%2/Fe3O4Magnetic nanometer composite material, mark
It is denoted as MoS2/Fe3O4(37.5wt%), specific surface area 17.5m2/ g, granularity 180nm, yield 92.6%, purity are
94.3%.
Embodiment 4
It is prepared according to the preparation method of embodiment 1, difference from example 1 is that, ferriferrous oxide nano
The amount that particle dispersion is added is 8mL, obtains Fe3O4Content is the MoS of 50wt%2/Fe3O4Magnetic nanometer composite material, label
For MoS2/Fe3O4(50wt%), specific surface area 17.5m2/ g, granularity 190nm, yield 92.3%, purity are
93.5%.
Reference examples 1
Low whipping speed be 500r/min under conditions of, by 10mL concentration be 0.01mol/L sodium molybdate solution with 15 drop/
The speed of minute is at the uniform velocity added drop-wise in the L-cysteine solution that concentration is 0.01mol/L, is continued to stir 30min, be mixed
Solution；
Mixed solution is added in reaction kettle, 80min is stirred, then carries out hydrothermal synthesis reaction under the conditions of 180 DEG C
For 24 hours, gained system is then centrifuged 10min under the conditions of 8000r/min, obtained solid material is used into pure water and dehydrated alcohol
It alternately washs 4 times altogether, is then dissolved in dehydrated alcohol and dries, obtain flower pattern MoS2Material.
Application examples 1
MoS prepared by the Examples 1 to 4 of 3mg2/Fe3O4MoS prepared by magnetic nanometer composite material, reference examples 12Material
Material and Fe3O4Material, i.e. MoS2/Fe3O4(12.5wt%), MoS2/Fe3O4(25wt%), MoS2/Fe3O4(37.5wt%),
MoS2/Fe3O4(50wt%), MoS2、Fe3O4Progress ultrasonic disperse 5min in conical flask, transfer are added to 50mL pure water respectively
Into the quartz test tube of 80mL, it is placed in photochemical reaction instrument, opening circulating condensing water stablizes temperature in device in room temperature,
Sample is placed in dark under the premise of not opening 800w xenon lamp, magnetic agitation 30min is carried out with the speed of 300r/min, with true
The adsorption-desorption for protecting TC and photocatalyst surface reaches balance；After reaching adsorption-desorption balance, it is added into reaction vessel
The hydrogen peroxide that 0.11mL mass fraction is 30% opens light source, is centrifuged, adopts at interval of 4min sampling 4mL supernatant
The concentration of TC in gained supernatant is measured with ultraviolet specrophotometer；The photocatalytic degradation efficiency calculation formula of TC is as follows:
The photocatalytic degradation efficiency of TC=(1-Ct/Co) × 100%,
In formula, C0For the initial concentration 30mg/L of TC；
CtFor the concentration of TC in different moments supernatant to be measured.
The MoS of Examples 1 to 4 preparation2/Fe3O4Magnetic nanometer composite material, reference examples 1 prepare MoS2Material and Fe3O4Material
Expect in different moments to the photocatalytic degradation efficiency of TC as shown in table 1, Fig. 4 and Fig. 5:
1 Examples 1 to 4 of table, reference examples 1, Fe3O4The degradation rate of catalytic degradation TC
By table 1, Fig. 4 and Fig. 5 it is found that under identical experiment condition, MoS prepared by the present invention2/Fe3O4Magnetic Nano is multiple
Condensation material is significantly larger than single MoS to the photocatalytic degradation efficiency of TC2Material and Fe3O4Material, and work as MoS2/Fe3O4Magnetic
Fe in property nanocomposite3O4Mass fraction be 25% when, i.e. MoS2/Fe3O4The photocatalytic degradation efficiency of (25wt%) is most
A height of 99.84%, close to 100%, test result is as shown in Figures 4 and 5.Show MoS prepared by the present invention2/Fe3O4Magnetic Nano
Composite material is extremely strong to the photocatalytic activity of TC.
Application examples 2
In order to verify MoS2/Fe3O4Photocatalytic activity cyclic utilization rate of the magnetic nanometer composite material to TC, the invention of this hair
By MoS2/Fe3O4The carry out light degradation experiment of (25wt%) to TC, will be to the MoS obtained after TC degradation 70min2/Fe3O4
(25wt%) is dried using alternately washing 4 times of water, dehydrated alcohol, obtains recycling MoS2/Fe3O4(25wt%) magnetic Nano is compound
Material；Then MoS will be recycled again2/Fe3O4(25wt%) magnetic nanometer composite material carries out light degradation to TC solution again；Circulation
Using 5 times, the photocatalytic degradation efficiency to TC is respectively 99.84%, 98.15%, 97.55%, 97.15%, 96.34%.
Fig. 6 is MoS2/Fe3O4Cyclical stability effect of (25wt%) magnetic nanometer composite material to TC photocatalytic degradation
Figure, wherein 70min, 140min, 210min, 280min, 350min successively indicates to follow magnetic nanometer composite material ring utilize the 1st,
2,3,4,5 times.It will be appreciated from fig. 6 that after MoS2/Fe3O4 magnetic nanometer composite material prepared by the present invention recycles 5 times, to TC
Photocatalytic degradation efficiency 96% or more, reduced by only 3.5%, show that MoS2/Fe3O4 magnetic Nano provided by the invention is multiple
Condensation material cyclic utilization rate is high, stability is good, is suitble to practical application.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of molybdenum disulfide/ferroferric oxide magnetic nano composite material, which is characterized in that be flower type structure, including two sulphur
Change molybdenum and combines to obtain with the ferroso-ferric oxide for being supported on molybdenum disulfide surface；It is formed between the molybdenum disulfide and ferroso-ferric oxide
Hetero-junctions.
2. molybdenum disulfide/ferroferric oxide magnetic nano composite material according to claim 1, which is characterized in that described two
The mass fraction of ferroso-ferric oxide is 10~60% in molybdenum sulfide/ferroferric oxide magnetic nano composite material.
3. molybdenum disulfide as claimed in claim 1 or 2/ferroferric oxide magnetic nano composite material preparation method, feature exist
In, comprising the following steps:
L-cysteine solution, sodium molybdate solution and ferroferric oxide nano granules dispersion liquid are mixed, it is anti-to carry out hydrothermal synthesis
It answers, obtains molybdenum disulfide/ferroferric oxide magnetic nano composite material.
4. preparation method according to claim 3, which is characterized in that the concentration of the L-cysteine solution be 0.01~
0.03mol/L；The concentration of the sodium molybdate solution is 0.01~0.03mol/L；The ferroferric oxide nano granules dispersion liquid
Concentration be 8~12mg/L.
5. preparation method according to claim 4, which is characterized in that the L-cysteine solution, sodium molybdate solution and four
The volume ratio of Fe 3 O nanoparticulate dispersion is 1:(0.8~1.2): (0.05~0.8).
6. according to any one of claim 3~5 preparation method, which is characterized in that the ferroferric oxide nano granules point
The granularity of ferroferric oxide nano granules is 150~200nm in dispersion liquid.
7. preparation method according to claim 3, which is characterized in that the reaction temperature of the hydrothermal synthesis reaction be 150~
200 DEG C, the reaction time is 12~36h.
8. preparation method according to claim 3, which is characterized in that the mixed mode is to be added drop-wise to sodium molybdate solution
It is mixed in L-cysteine solution, ferroferric oxide nano granules dispersion liquid is then added in gained mixed system.
9. preparation method according to claim 8, which is characterized in that the speed of the dropwise addition is 7~20 drops/minute.
10. any one of the claim 1~2 molybdenum disulfide/ferroferric oxide magnetic nano composite material or claim 3~
Molybdenum disulfide/ferroferric oxide magnetic nano composite material that any one of 9 preparation methods obtain is organic in photocatalytic degradation
Application in pollutant.
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