CN104588044B - Quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR visible light catalytic composite nano materials and preparation technology - Google Patents
Quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR visible light catalytic composite nano materials and preparation technology Download PDFInfo
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Abstract
The present invention relates to quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR efficient visible light catalysis composite nano materials and preparation technology thereof.Adopt functionalized ion liquid self-assembly method, by water-heat process, soxhlet extraction, Low Temperature Heat Treatment by CdSeMT load in graphene base body.The outstanding feature of the method is: the preparation of application function ionic liquid self-assembly method has the quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR efficient visible light catalysis composite nano materials of novel structure and good physical chemical property.For TiO
2the application study of class catalysis material provides a new approach.Present invention process is simple, is easy to suitability for industrialized production, prepared meso-porous nano material, and specific area is large, even aperture distribution, visible light catalytic performance are good.
Description
Technical field
The present invention relates to quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR visible light catalytic composite nano materials and preparation technology, belong to field of functional materials.
Background technology
The Control and treatment of environmental pollution is that human social must face and key subjects urgently to be resolved hurrily.Photocatalysis engineering directly utilizes low-density solar energy to be converted into energy needed for chemical reaction, and being used for degrading and the advanced technology of the various pollutant of mineralising, is the effective means of solution problem of environmental pollution.TiO
2because of its biologically inert and chemical inertness, photoetch and chemical attack can not be there is, the advantage such as cheap, and be proved to be a kind of photochemical catalyst of being most widely used.Due to TiO
2electron distributions be characterised in that the existence having band gap between its conduction band and valence band.When being subject to illumination, as long as the energy of photon equals or exceeds the band-gap energy (h ν>=E of semiconductor
g), electronics just can be made to transit to conduction band from valence band, thus produce conduction band electron and valence band hole.Under the electric field action of space charge layer, the oxidation component that the free electron of conduction band moves to rapidly semiconductive particles surface and is transferred in solution, thus light induced electron and hole form hydroxyl radical free radical OH through series reaction, it can be oxidized nearly all organic matter.Therefore, it has powerful application prospect at field of Environment Protection (as exhaust-gas treatment).Course of reaction is as follows:
TiO
2+hν→h
++e
-
H
2O+h
+→·OH+H
+
e
-+O
2→O
2 -·
H
++O
2 -·→HO
2·
2HO
2·→H
2O
2+O
2
H
2O
2+O
2 -·→·OH+OH
-+O
2
h
++OH
-→·OH
H
++ org → intermediate → CO
2+ H
2o
OH+org → intermediate → CO
2+ H
2o
But, due to TiO
2greater band gap (about 3.2eV), its threshold wave-length absorbed is less than 400nm, not high to the utilization rate of sunshine; Have impact on TiO
2practical and the industrialization process of multiphase photocatalysis reaction.In addition, also there is light induced electron and hole easily in problems such as material surface compounds, have impact on TiO
2practical and the industrialization process of multiphase photocatalysis reaction.Research finds, by TiO2 finishing, as noble metal surface deposition, semiconductor doping and quantum dot (Quantumdot, QD) sensitization, can improve TiO
2photocatalytic activity and visible ray utilization rate.Because quantum dot has the following advantages as sensitizer tool: 1) level structure can be regulated by the size controlling quantum dot, enable its absorption spectrum mate sunshine spectrum; 2) natural dipole moment of semiconductor-quantum-point can make electric charge quick separating; 3) quantum dot absorbs a photon and can produce multiple light induced electron.Therefore, quantum dot sensitized TiO
2nano-photocatalyst material also just one of study hotspot becoming photocatalysis field.But, the adhesion that the quantum dot sensitized complex of surface state exists between quantum dot with matrix is relative poor, and quantum dot is exposed in reactant and surrounding medium, the corrosion Sum decomposition in course of reaction, cause it easily to come off, affect and limit its practical application.For this reason, form so-called nucleocapsid structure at quantum dot surface epitaxial growth one deck shell material, can the surface of effective passivation quantum dot, reduce the sensitiveness of quantum dot environmental change to external world, surface chemistry and photooxidation, improve stability and optical property.Therefore, nucleocapsid cladded type complex becomes quantum dot sensitized research and development direction.In addition, due to crystallite dimension, brilliant bag parameter, current quantum dot sensitized complex ubiquity quantum dot is reunited, quantum dot does not mate with matrix, compatibility, heterofilm resistivity is caused to increase, be unfavorable for Charger transfer, photoelectric transformation efficiency declines, photocatalytic activity and photocatalysis efficiency are not high, affect yet and constrain its industrial production and practical application.For this reason, the two-dimension plane structure utilizing Graphene regular in recent years and high conductivity, improve the mobility of light induced electron in semiconductor, reduces the recombination probability of carrier, i.e. quantum dot sensitized graphene-based TiO
2the preparation of catalysis material and performance study receive the great attention of people, become the important front edge problem of photocatalysis field.
But up to now, a large amount of work also mainly concentrates on the quantum dot sensitized graphene-based TiO of surface state
2film and for solar cell aspect, we know, relative to fiber and film, mesoporous TiO
2material is widely used in catalysis, separation, sensor field due to its bigger serface, controllable bore diameter and even duct.The assembling of quantum dot and mesoporous material, not only makes their numerous characteristics be not fully exerted, and creates again them and itself do not possess much character.Therefore, by quantum dot to mesoporous TiO
2functionalization to realize visible light catalytic be one of study hotspot of current catalytic field.
But it is worth noting, also not preparing with quantum dot is so far sensitizer, in conjunction with Graphene high conduction performance and the coated characteristic of meso-porous nano material, that is, the graphene-based mesoporous cladded type titanium oxide (mesoporousTiO of CdSe quantum dot sensitization
2– coatedongraphenewithCdSequantumdots; (CdSeMT/GR) effective ways of composite Nano catalysis material.
Summary of the invention
Technical problem to be solved by this invention is: solve above-mentioned prior art Problems existing, and providing that a kind of specific area is large, cementability good, visible light catalytic is good, preparation technology is simple, the quantum dot sensitized graphene-based mesoporous cladded type CdSeMT/GR efficient visible light catalysis composite nano materials and the preparation technology thereof that are easy to suitability for industrialized production.
The technical solution used in the present invention is: adopt functionalized ion liquid (IonicLiquids, IL) self-assembly method, first the bifunctional molecule of ionic liquid is utilized to modify quantum dot, functionalized ion liquid template is formed by the compound assembling of electrostatic, recycle its micella mutually gathered together and polymerizable inorganic source independently to fill under certain synthetic environment and generate the coated functionalization complex of inorganic source, pass through soxhlet extraction subsequently, while Low Temperature Heat Treatment removes the mesoporous and crystallization of template generation, again quantum dot is fixed on mesoporous in, complete quantum dot sensitized mesoporous coated CdSeMT composite nanometer particle synthesis, finally by water-heat process, realize CdSeMT load in graphene base body, synthesize quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR efficient visible light catalysis composite nano materials.
In technique scheme, concrete preparation technology is:
(1) with octadecylene, aliphatic acid (such as oleic acid, palmitic acid, stearic acid etc.), solvent (such as halogenated alkane, as chloroform), CdO, Se powder is raw material, by solvent-thermal method at temperature range 60-90 DEG C, preferably stir process (preferably more than 20 minutes at 70 ~ 85 DEG C, preferably more than 30 minutes, such as 30 minutes ~ 2 hours, preferred 30-60min, synthesis CdSe quantum dot, adopt ultrasonic mixing (such as 20 minutes ~ 2 hours time, preferably 25 ~ 30min, ultrasonic power 50W ~ 100W, preferably about 70W), (ionic liquid is selected from alkyl quaternary ammonium ion liquid to use ionic liquid, Wan Ji quaternary phosphine ionic liquid, 1, the imidazole ion liquid that 3-dialkyl group replaces, the pyridine ion liquid that N-alkyl replaces), by above-mentioned CdSe quantum dot by electrostatic complex group equipment complex functionality IL – CdSe solution,
(2) with IL – CdSe be template, titanate esters (such as butyl titanate) is for inorganic source, hydrochloric acid is catalyst, by above three's mixing (preferably temperature 30 ~ 80 DEG C, preferably 35 ~ 45 DEG C, more preferably at 40 DEG C, mixing speed preferably 100 turns/min ~ 500 turn/min, preferably about 200 revs/min; Mixing time more than 30 minutes, such as 30 minutes ~ 200 minutes, preferably 60 minutes ~ 120 minutes, more preferably from about 100min), prepare quantum dot sensitized ions liquid inorganic source coated functionalization IL – CdSeTi inorganic source sol by solation self assembly;
(3) take Graphene as base material, above-mentioned quantum dot sensitized ionic liquid inorganic source coated functionalization IL – CdSeTi inorganic source sol and Graphene are carried out hydrothermal treatment consists (hydrothermal conditions: 2 ~ 10 hours time, preferred 3-7h, pressure 1 ~ 12MPa, preferably about 2 – 10MPa, temperature 180 ~ 320 DEG C, preferably about 200 – 300 DEG C), prepare quantum dot sensitized graphene-based " IL – CdSe " Ti inorganic source/GR complex, wherein Graphene is relative to weight ratio=1:1 ~ 4 of IL – CdSeTi inorganic source sol, , preferred about 1:1 ~ 3, more preferably preferred about 1:2,
(4) extractant (low-molecular-weight organic matter such as methyl alcohol and ethanol) is used, adopt soxhlet extraction by template removing in IL – CdSeTi inorganic source/GR, then by Low Temperature Heat Treatment, mesoporous quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR efficient visible light catalysis composite nano materials is prepared.
Preferably, in step (1), according to octadecylene: aliphatic acid (oleic acid): solvent (chloroform): CdO:Se powder=1 ~ 5:2 ~ 8:0.5 ~ 2:0.5 ~ 2, preferably 2 ~ 4:3 ~ 7:0.8 ~ 1.2:0.8 ~ 1.2, the more preferably weight ratio of 3:5:1:1; Weight ratio=1:0.5 ~ 5 of ionic liquid: CdSe, preferred 1:2 ~ 3, more preferably 1:2.
Preferably, in step (2), titanate esters (such as butyl titanate): concentrated hydrochloric acid: weight ratio=10 ~ 15:0.1 ~ 3:1 ~ 14 of IL – CdSe solution, preferably 11 ~ 14:0.3 ~ 1:3 ~ 12, more preferably 10-13:0.4-0.6:9-12.
In technique scheme, preferably, agents useful for same is: butyl titanate, purity > 99.0%; Hydrochloric acid, concentration > 37%.
In technique scheme, soxhlet extraction condition, extraction times 2 – 8 times, each extraction time 30 – 120min, extraction temperature 70-90 DEG C.
In technique scheme, Low Temperature Heat Treatment condition, temperature 180 – 300 DEG C, preferably about 200 ~ 250 DEG C, more than 25 minutes time, preferably about 30 minutes ~ 3 hours, more preferably from about 30-90min.
In technique scheme, hydrothermal condition is preferably 2 ~ 10 hours time, preferred 3-7h, pressure 1 ~ 12MPa, is more preferably time 3-7h, pressure 2 – 10MPa, temperature 200 – 300 DEG C.
In technique scheme, functionalized ion liquid is preferably synthesized by N-alkylpyridiniium cation and CdSe quantum dot.
Invention additionally provides the quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR efficient visible light catalysis composite nano materials obtained by above-mentioned preparation technology.
The present invention adopts functionalized ion liquid self-assembly method, by water-heat process, soxhlet extraction and Low Temperature Heat Treatment synthesis CdSeMT/GR efficient visible light catalysis composite nano materials.At present, we utilized this technique to prepare quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR composite nano materials has following remarkable advantage: (a) specific area is large, has efficient visible light catalytic performance; B () pore structure can adjust, can carry out Quantitative design; C () cohesive force is strong, processing technology is good; D () calcining heat is low, preparation technology is simple, and production cost is low, is easy to suitability for industrialized production; E () is widely used, be to solve photocatalysis technology to be applied to the most effective material of poisonous and harmful substance degraded, decreases poisonous and harmful substance degradation treatment cost.
CdSeMT/GR efficient visible light catalysis composite nano materials physical and chemical performance
After functionalized ion liquid self assembly, water-heat process, soxhlet extraction and Low Temperature Heat Treatment, its crystalline structure of CdSeMT/GR is anatase, and crystallite dimension is between 3-7nm; Surface topography relatively evenly, have obvious central hole structure, defect few; Compare the pure TiO of P25
2powder, has obvious UV absorption turning, achieves visible absorption near 400nm; O-H linkage content is relatively high.Specific area is large, voidage is high, efficient visible light catalytic performance.
Accompanying drawing explanation
Fig. 1 preparation technology's schematic diagram of the present invention.
Mesoporous coated CdSeMT/GR composite nano materials transmission electron microscope (a) of Fig. 2 and ESEM (b) photo.
The X-ray diffractogram of the mesoporous coated CdSeMT/GR composite nano materials of Fig. 3.
The infared spectrum of the mesoporous coated CdSeMT/GR composite nano materials of Fig. 4.
Detailed description of the invention
Below by way of specific embodiment, the present invention is described.But the present invention does not limit by these embodiments.It will be appreciated by those skilled in the art that in the case without departing from the gist of the present invention, can make the present invention and suitably changing or adjustment, these changes or adjustment are also included into the present invention and protect category.
1) ultrasonic mixing is adopted, by ionic liquid N-alkylpyridiniium cation and Quantum dots CdS e, by electrostatic complex group equipment complex functionality IL – CdSe solution; Be inorganic source as template, with butyl titanate, adopt hydrochloric acid reaction speed, by under solation self assembly effect, synthesis IL – CdSTi inorganic source colloidal sol.Ionic liquid N-alkylpyridiniium cation and Quantum dots CdS e first together with add in there-necked flask, and butyl titanate and hydrochloric acid are added by funnel, and rate of addition general control is at 0.2 – 0.6mlmin
-1between; Synthesis IL – CdSTi inorganic source;
2) IL – CdSeTi inorganic source is put into hydrothermal reactor together with Graphene base material, by water-heat process synthesis IL – CdSeTi inorganic source/GR complex, hydrothermal condition, time 3-7h, pressure 2 – 10MPa, temperature 200 – 300 DEG C.
3) IL – CdSTi inorganic source/GR is put into soxhlet's extractor, extraction times 2 – 8 times, each extraction time 30 – 120min, extraction temperature 70-90 DEG C, making organic formwork completely be extracted out, for improving electrode crystal property, passing through Low Temperature Heat Treatment, temperature 200 – 300 DEG C, time 30-90min; Prepare the sensitized meso-porous coated CdSeMT/GR composite nano materials of quantum dot;
4) test analysis is carried out to the chemical form etc. of CdSeMT/GR specific area, aperture, crystal formation, surface topography, element, visible light catalytic performance is tested.
Embodiment 1: first with octadecylene, oleic acid, chloroform, CdO, Se powder for raw material, according to weight ratio octadecylene: oleic acid: chloroform: CdO:Se powder=3:5:1:1, under temperature 70 C, in oleic acid solvent, synthesize CdSe quantum dot by stirring 30min by solvent-thermal method.Adopt ultrasonic wave mixing (condition of mixing: time 30min, ultrasonic power 70W), make N-alkylpyridiniium cation (N-butyl-pyridinium tetrafluoro boric acid saline solution, 20ml, 17mgL by electrostatic self-assembled effect
-1) and above CdSe quantum dot (30ml, the 3umolL prepared
-1) form functionalization IL – CdSe.Secondly, this functionalization IL – CdSe is incorporated in there-necked flask, adopt and dissolve self assembling process, by 60g purity be 99.0% butyl titanate and 2ml concentrated hydrochloric acid (37 quality %) mixing after, be added drop-wise in above-mentioned there-necked flask, at 40 DEG C, continue ultrasonic agitation, form IL – CdSeTi inorganic source colloidal sol.IL – CdSeTi inorganic source colloidal sol is joined in hydrothermal reaction kettle, again 50g Graphene is put into this hydrothermal reaction kettle, under the condition of temperature 200 DEG C, time 3h, pressure 3MPa, obtain IL – CdSeTi inorganic source/GR complex, then put it in soxhlet's extractor, use ethanol extraction number of times 2 times, each extraction time 40min, extraction temperature 70 DEG C, finally, carry out Low Temperature Heat Treatment, temperature 200 DEG C, time 60min.Obtain CdSeMT/GR efficient visible light catalysis composite nano materials.Its crystal formation is anatase, and nano particle aperture size is 2 – 4nm, and specific area is 127m
2/ g.Fig. 2 shows this mesoporous coated CdSeMT/GR composite nano materials transmission electron microscope (a) and ESEM (b) photo.Fig. 3 shows the X-ray diffractogram of mesoporous coated CdSeMT/GR composite nano materials.Fig. 4 shows the infared spectrum of mesoporous coated CdSeMT/GR composite nano materials.
This type catalyst prepared above is degraded to standard solid thing rhodamine B (5g/L) solution under visible light, as long as the degradation rate of 100min rhodamine B is up to 99%, and after reusing 200 times in performance test, the degradation rate of 100min rhodamine B is also up to 95%, higher 2 times than similar P25 titanium oxide modified product performance.
Embodiment 2: first with octadecylene, oleic acid, chloroform, CdO, Se powder for raw material, according to weight ratio octadecylene: oleic acid: chloroform: CdO:Se powder=3:6:1:1.2, under temperature 70 C, in oleic acid solvent, synthesize CdSe quantum dot by stirring 30min by solvent-thermal method.Adopt ultrasonic wave mixing (condition of mixing: time 30min, ultrasonic power 70W), make N-alkylpyridiniium cation (N-butyl-pyridinium villaumite, 20ml, 17mgL by electrostatic self-assembled effect
-1) and above CdSe quantum dot (30ml, the 3umolL prepared
-1) form functionalization IL – CdSe.Secondly, this functionalization IL – CdSe is incorporated in there-necked flask, adopts and dissolve self assembling process, by 60g purity be 99.0% butyl titanate and 2ml concentrated hydrochloric acid (37 quality %) mixing after, be added drop-wise in this there-necked flask, continue ultrasonic agitation, form IL – CdSeTi inorganic source.IL – CdSeTi inorganic source colloidal sol is joined in hydrothermal reaction kettle, then 50g Graphene is put into this hydrothermal reaction kettle, under the condition of temperature 250 DEG C, time 5h, pressure 4MPa, obtain IL – CdSeTi inorganic source/GR complex, then, put it in soxhlet's extractor, adopt ethanol extraction number of times 2 times, each extraction time 50min, extraction temperature 70 DEG C, finally, carries out Low Temperature Heat Treatment, temperature 200 DEG C, time 70min.Obtain CdSeMT/GR efficient visible light catalysis composite nano materials.Its crystal formation is anatase, and nano particle aperture size is 3 – 7nm, and specific area is 121m
2/ g.
This type catalyst prepared above is degraded to standard solid thing rhodamine B (5g/L) solution under visible light, as long as the degradation rate of 100min rhodamine B is up to 99%, and after reusing 200 times in performance test, the degradation rate of 100min rhodamine B is also up to 95%, higher 2 times than similar P25 titanium oxide modified product performance.
Embodiment 3: first with octadecylene, oleic acid, chloroform, CdO, Se powder for raw material, according to weight ratio octadecylene: oleic acid: chloroform: CdO:Se powder=3:5:1:1, under temperature 70 C, in oleic acid solvent, synthesize CdSe quantum dot by stirring 30min by solvent-thermal method.Adopt ultrasonic wave mixing (condition of mixing: time 30min, ultrasonic power 70W), make N-alkylpyridiniium cation (N-hexyl pyridine villaumite, 20ml, 17mgL by electrostatic self-assembled effect
-1) and above CdSe quantum dot (30ml, the 3umolL prepared
-1) form functionalization IL – CdSe.Secondly, this functionalization IL – CdSe is incorporated in there-necked flask, adopts and dissolve self assembling process, by 60g purity be 99.0% butyl titanate and the mixing of 2ml concentrated hydrochloric acid after, be added drop-wise in this there-necked flask, continue ultrasonic agitation, form IL – CdSeTi inorganic source.IL – CdSeTi inorganic source colloidal sol is joined in hydrothermal reaction kettle, then 50g Graphene is put into this hydrothermal reaction kettle, under the condition of temperature 200 DEG C, time 6h, pressure 2MPa, obtain IL – CdSeTi inorganic source/GR complex, then, put it in soxhlet's extractor, adopt ethanol extraction number of times 6 times, each extraction time 40min, extraction temperature 70 DEG C, finally, carries out Low Temperature Heat Treatment, temperature 200 DEG C, time 30min.Obtain the mesoporous covered composite yarn nano particle of CdSeMT.Finally, CdSeMT/GR efficient visible light catalysis composite nano materials will be obtained.Its crystal formation is anatase, and nano particle aperture size is 1 – 3nm, and specific area is 137m
2/ g.
This type catalyst prepared above is degraded to standard solid thing rhodamine B (5g/L) solution under visible light, as long as the degradation rate of 100min rhodamine B is up to 99%, and after reusing 200 times in performance test, the degradation rate of 100min rhodamine B is also up to 95%, higher 2 times than similar P25 titanium oxide modified product performance.
Embodiment 4: first with octadecylene, oleic acid, chloroform, CdO, Se powder for raw material, according to weight ratio octadecylene: oleic acid: chloroform: CdO:Se powder=3:5:1:1, under temperature 70 C, in oleic acid solvent, synthesize CdSe quantum dot by stirring 30min by solvent-thermal method.Adopt ultrasonic wave mixing (condition of mixing: time 30min, ultrasonic power 70W), make N-alkylpyridiniium cation (N-octylpyridinium villaumite, 20ml, 17mgL by electrostatic self-assembled effect
-1) and CdSe quantum dot (30ml, 3umolL
-1) form functionalization IL – CdSe, secondly, this functionalization IL – CdSe is incorporated in there-necked flask, adopt and dissolve self assembling process, by 60g purity be 99.0% butyl titanate and 2ml concentrated hydrochloric acid alcohol mixing after, be added drop-wise in this there-necked flask, continue ultrasonic agitation, form IL – CdSeTi inorganic source.IL – CdSeTi inorganic source colloidal sol is joined in hydrothermal reaction kettle, then 5mg Graphene is put into hydrothermal reaction kettle, under the condition of temperature 200 DEG C, time 6h, pressure 2MPa, obtain IL – CdSeTi inorganic source/GR complex, then, put it in soxhlet's extractor, adopt ethanol extraction number of times 2 times, each extraction time 120min, extraction temperature 70 DEG C, finally, carries out Low Temperature Heat Treatment, temperature 300 DEG C, time 90min.Obtain CdSeMT/GR efficient visible light catalysis composite nano materials.Its crystal formation is anatase, and nano particle aperture size is 1 – 3nm, and specific area is 119m
2/ g.
This type catalyst prepared above is degraded to standard solid thing rhodamine B (5g/L) solution under visible light, as long as the degradation rate of 100min rhodamine B is up to 99%, and after reusing 200 times in performance test, the degradation rate of 100min rhodamine B is also up to 95%, higher 2 times than similar P25 titanium oxide modified product performance.
Embodiment 5: first with octadecylene, oleic acid, chloroform, CdO, Se powder for raw material, according to weight ratio octadecylene: oleic acid: chloroform: CdO:Se powder=3:5:1:1, under temperature 70 C, in oleic acid solvent, synthesize CdSe quantum dot by stirring 30min by solvent-thermal method.Adopt ultrasonic wave mixing (condition of mixing: time 30min, ultrasonic power 70W), make N-alkylpyridiniium cation (N-butyl-pyridinium tetrafluoro boric acid saline solution, 20ml, 17mgL by electrostatic self-assembled effect
-1) and CdSe quantum dot (30ml, 3umolL
-1) form functionalization IL – CdSe.Secondly, this functionalization IL – CdSe is incorporated in there-necked flask, adopts and dissolve self assembling process, by 60g purity be 99.0% butyl titanate and the mixing of 2ml concentrated hydrochloric acid alcohol after, be added drop-wise in this there-necked flask, continue ultrasonic agitation, form IL – CdSeTi inorganic source.IL – CdSeTi inorganic source colloidal sol is joined in hydrothermal reaction kettle, then 50g Graphene is put into hydrothermal reaction kettle, under the condition of temperature 300 DEG C, time 6h, pressure 2MPa, obtain " IL – CdSe " Ti inorganic source/GR complex, then, put it in soxhlet's extractor, adopt ethanol extraction number of times 8 times, each extraction time 40min, extraction temperature 80 DEG C, finally, carries out Low Temperature Heat Treatment, temperature 200 DEG C, time 30min.Obtain CdSeMT/GR efficient visible light catalysis composite nano materials.Its crystal formation is anatase, and nano particle aperture size is 3 – 6nm, and specific area is 131m
2/ g.
This type catalyst prepared above is degraded to standard solid thing rhodamine B (5g/L) solution under visible light, as long as the degradation rate of 100min rhodamine B is up to 99%, and after reusing 200 times in performance test, the degradation rate of 100min rhodamine B is also up to 95%, higher 2 times than similar P25 titanium oxide modified product performance.
Embodiment 6: first with octadecylene, oleic acid, chloroform, CdO, Se powder for raw material, according to weight ratio octadecylene: oleic acid: chloroform: CdO:Se powder=3:5:1:1, under temperature 70 C, in oleic acid solvent, synthesize CdSe quantum dot by stirring 30min by solvent-thermal method.Adopt ultrasonic wave mixing (condition of mixing: time 30min, ultrasonic power 70W), make N-alkylpyridiniium cation (N-butyl-pyridinium tetrafluoro boric acid saline solution, 20ml, 17mgL by electrostatic self-assembled effect
-1) and CdSe quantum dot (30ml, 3umolL
-1) form functionalization IL – CdSe.Secondly, this functionalization IL – CdSe is incorporated in there-necked flask, adopts and dissolve self assembling process, by 60g purity be 99.0% butyl titanate and the mixing of 2ml concentrated hydrochloric acid alcohol after, be added drop-wise in this there-necked flask, continue ultrasonic agitation, form IL – CdSeTi inorganic source.IL – CdSeTi inorganic source colloidal sol is joined in hydrothermal reaction kettle, then 50g Graphene is put into hydrothermal reaction kettle, under the condition of temperature 250 DEG C, time 4h, pressure 4MPa, obtain IL – CdSeTi inorganic source/GR complex, then, put it in soxhlet's extractor, adopt ethanol extraction number of times 2 times, each extraction time 40min, extraction temperature 90 DEG C, finally, carries out Low Temperature Heat Treatment, temperature 300 DEG C, time 30min.Obtain CdSeMT/GR efficient visible light catalysis composite nano materials.Its crystal formation is anatase, and nano particle aperture size is 2 – 5nm, and specific area is 137m
2/ g.
This type catalyst prepared above is degraded to standard solid thing rhodamine B (5g/L) solution under visible light, as long as the degradation rate of 100min rhodamine B is up to 99%, and after reusing 200 times in performance test, the degradation rate of 100min rhodamine B is also up to 95%, higher 2 times than similar P25 titanium oxide modified product performance.
Embodiment 7: first with octadecylene, oleic acid, chloroform, CdO, Se powder for raw material, according to weight ratio octadecylene: oleic acid: chloroform: CdO:Se powder=3:5:1:1, under temperature 70 C, in oleic acid solvent, synthesize CdSe quantum dot by stirring 30min by solvent-thermal method.Adopt ultrasonic wave mixing (condition of mixing: time 30min, ultrasonic power 70W), make N-alkylpyridiniium cation (N-butyl-pyridinium tetrafluoro boric acid saline solution, 20ml, 17mgL by electrostatic self-assembled effect
-1) and CdSe quantum dot (30ml, 3umolL
-1) form functionalization IL – CdSe.Secondly, this functionalization IL – CdSe is incorporated in there-necked flask, adopts and dissolve self assembling process, by 60g purity be 99.0% butyl titanate and the mixing of 2ml concentrated hydrochloric acid alcohol after, be added drop-wise in this there-necked flask, continue ultrasonic agitation, form IL – CdSeTi inorganic source.IL – CdSeTi inorganic source colloidal sol is joined in hydrothermal reaction kettle, then 50g Graphene is put into hydrothermal reaction kettle, under the condition of temperature 200 DEG C, time 5h, pressure 3MPa, obtain IL – CdSeTi inorganic source/GR complex, then, put it in soxhlet's extractor, adopt ethanol extraction number of times 2 times, each extraction time 40min, extraction temperature 70 DEG C, finally, carries out Low Temperature Heat Treatment, temperature 200 DEG C, time 60min.Obtain CdSeMT/GR efficient visible light catalysis composite nano materials.Its crystal formation is anatase, and nano particle aperture size is 3 – 6nm, and specific area is 149m
2/ g.
This type catalyst prepared above is degraded to standard solid thing rhodamine B (5g/L) solution under visible light, as long as the degradation rate of 100min rhodamine B is up to 99%, and after reusing 200 times in performance test, the degradation rate of 100min rhodamine B is also up to 95%, higher 2 times than similar P25 titanium oxide modified product performance.
Claims (11)
1. the preparation technology of quantum dot sensitized graphene-based mesoporous cladded type CdSeMT/GR visible light catalytic composite nano materials, it comprises:
(1) with octadecylene, aliphatic acid, solvent, CdO, Se powder for raw material, by solvent-thermal method stir process at temperature range 60-90 DEG C, synthesis CdSe quantum dot, then ultrasonic mixing is adopted, use ionic liquid, by CdSe quantum dot by electrostatic complex group equipment complex functionality IL – CdSe solution;
(2) with IL – CdSe be template, titanate esters for inorganic source, hydrochloric acid is catalyst, above three is mixed, and prepares quantum dot sensitized ions liquid inorganic source coated functionalization IL – CdSeTi inorganic source sol by solation self assembly;
(3) take Graphene as base material, quantum dot sensitized ionic liquid inorganic source coated functionalization IL – CdSeTi inorganic source sol step (2) obtained and Graphene carry out hydrothermal treatment consists, prepare quantum dot sensitized graphene-based IL – CdSeTi inorganic source/GR complex, wherein Graphene is relative to weight ratio=1:1 ~ 4 of IL – CdSeTi inorganic source sol;
(4) use extractant, adopt soxhlet extraction by template removing in IL – CdSeTi inorganic source/GR, then by Low Temperature Heat Treatment, prepare mesoporous quantum dot sensitized graphene-based mesoporous coated CdSeMT/GR visible light catalytic composite nano materials.
2. technique according to claim 1, wherein, in step (1), ionic liquid: weight ratio=1:0.5 ~ 5 of CdSe quantum dot; And/or
In step (2), titanate esters: concentrated hydrochloric acid: weight ratio=10 ~ 15:0.1 ~ 3:1 ~ 14 of IL – CdSe solution.
3. technique according to claim 1 and 2, wherein, in step (2), the titanate esters used is butyl titanate.
4. technique according to claim 1 and 2, wherein, Graphene is relative to weight ratio=1:1 ~ 3 of IL – CdSeTi inorganic source sol.
5. technique according to claim 1 and 2, wherein, described ionic liquid is selected from alkyl quaternary ammonium ion liquid, Wan Ji quaternary phosphine ionic liquid, the imidazole ion liquid of 1,3-dialkyl group replacement, the pyridine ion liquid of N-alkyl replacement.
6. technique according to claim 5, wherein, the condition that the ultrasonic mixing in step (1) adopts is 20 minutes ~ 2 hours time, ultrasonic power 50W ~ 100W.
7. technique according to claim 6, wherein, the hydrothermal conditions in step (3) is 2 ~ 10 hours time, pressure 1 ~ 12MPa, temperature 180 ~ 320 DEG C.
8. technique according to claim 7, wherein, soxhlet extraction condition is extraction times 2 – 8 times, each extraction time 30 – 120min, extraction temperature 70-90 DEG C.
9. technique according to claim 8, wherein, Low Temperature Heat Treatment condition is temperature 180 – 300 DEG C, 30 minutes ~ 3 hours time.
10. technique according to claim 9, wherein, Low Temperature Heat Treatment condition is temperature 200 ~ 250 DEG C, time 30-90min.
The 11. quantum dot sensitized graphene-based mesoporous cladded type CdSeMT/GR visible light catalytic composite nano materials prepared according to the technique of any one of claim 1-10.
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