CN106824287A - The preparation method of CdSe quantum dots and the composites of UIO 67 - Google Patents
The preparation method of CdSe quantum dots and the composites of UIO 67 Download PDFInfo
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- CN106824287A CN106824287A CN201710203158.2A CN201710203158A CN106824287A CN 106824287 A CN106824287 A CN 106824287A CN 201710203158 A CN201710203158 A CN 201710203158A CN 106824287 A CN106824287 A CN 106824287A
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical class [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001661 cadmium Chemical class 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000011049 filling Methods 0.000 claims abstract description 15
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000058 selane Inorganic materials 0.000 claims abstract description 15
- 230000001186 cumulative effect Effects 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000012159 carrier gas Substances 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- AMULVJPCIVLXGR-UHFFFAOYSA-N cadmium(2+) ethanol dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Cd+2].[N+](=O)([O-])[O-] AMULVJPCIVLXGR-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 5
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- OOCDCMOCRISZFC-UHFFFAOYSA-N cadmium ethanol Chemical compound [Cd].CCO OOCDCMOCRISZFC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002096 quantum dot Substances 0.000 abstract description 54
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 21
- 239000012621 metal-organic framework Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 octadecylene Chemical group 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000013177 MIL-101 Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011469 building brick Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention provides the preparation method of a kind of CdSe quantum dots and the composites of UIO 67, and it includes step：At normal temperatures and pressures, cadmium salt soln is distributed to inside UIO 67 in equal volume, by the use of inert gas as carrier gas by H2Se gases are transferred in the container for filling UIO 67, terminate reaction, through ethanol washing, vacuum drying, obtain CdSe quantum dots and the composites of UIO 67；Isometric dispersion refers to that the cumulative volume of the cadmium salt soln is equal with the volume of the solvent for dissolving cadmium salt that UIO 67 to be adsorbed.The preparation method of the CdSe quantum dots and the composites of UIO 67 can avoid cap from sealing reagent and produce influence to the catalytic performance of CdSe quantum dots and the composites of UIO 67, CdSe quantum dots and the composites of UIO 67 are prepared under normal temperature condition simultaneously, can avoid due in normative heat treatment technique temperature it is too high and produce without catalytic capability hexagonal phase CdSe quantum dot, while avoiding the skeleton structures of UIO 67 from rupturing.Additionally, preparation process is simple, product can be easily separated, raw material availability it is high.
Description
Technical field
It is combined the present invention relates to quantum dot synthetic method technical field, more particularly to a kind of CdSe quantum dots and UIO-67
The preparation method of material.
Background technology
The material referred to as MOF materials (metal being formed by connecting as node by organic ligand and metal ion or cluster
Organic open-framework material), this kind of material has the advantages that high-crystallinity, bigger serface, stable chemical nature, and its hole
Road and hole also have designability., Cavka, A new zirconium inorganic building brick in 2008
forming metal organic frameworks with exceptional stability,J.Am.Chem.Soc.,
130 (2008), 13850-13851 have reported a class by Zr6O4(OH)4(CO2)12Cluster constitute and skeleton include tetrahedron cage
With the compound of octahedra cage, referred to as UIO-66 and the like, when organic ligand is 4, during 4 '-biphenyl dicarboxylic acid, Cavka etc.
It is UIO-67 by this Compound nomenclature.UIO-67 chemical property is highly stable, can be placed in water several months structure and not change,
And its BET specific surface area is up to 2700m2/ g, therefore UIO-67 can be used as the carrier of load active component.
QD@MOF composites can be prepared by two lines：The first is by QD (quantum dot) and forms MOF materials
Raw material is mixed and then reaction generation MOF materials, while QD is wrapped up into the skeleton structure of the MOF materials of generation.By
It is very small in the particle diameter of initiation material QD, reagent (capping agent) encapsulation QD need to be sealed to avoid the group between QD using cap
It is poly-, therefore cap envelope reagent inevitably enters in the skeleton structure of MOF materials when MOF materials are synthesized.Because cap seals reagent
Presence, necessarily affect the photoelectric properties of QD@MOF composites.Such as CdSe/CdS/Cd0.5Zn0.5S/ZnS@MOF-5 are combined
Material is that the QD of cap envelope reagent encapsulation is together reacted with the presoma of synthesis MOF-5.Additionally, also CdTe@ZIF-8 are multiple
Condensation material is also to be prepared using the method.Second method is that the presoma of QD is assembled into MOF materials under certain conditions
Skeleton structure in, then prepared through Overheating Treatment (including hydrogenation or reduce).For metal quantum point, typical process is
Permeated by solution impregnation or gas and metal QD presomas are transferred in MOF materials, then by high temperature reduction or added
Hydrogen obtains QD MOF composites, and due to needing through Overheating Treatment, the skeleton structure of MOF materials may rupture.For changing
Compound quantum dot, it is also possible to obtained by heat-treating methods, such as CdSe@MIL-101 (Al)-NH2Composite be by
MIL-101(Al)-NH2503K is heated to CdO octadecylene solution, Se octadecylenes solution is then injected into and is obtained CdSe@MIL-101
(Al)-NH2Composite；Another example is CdS@MIL-101 composites, is incited somebody to action by Hydrothermal Synthesiss CdS quantum dot
MIL-101 is added and obtained.
In view of this, it is desirable to provide a kind of that cap envelope reagent will not be both introduced when MOF materials are synthesized, also will not be due to needing
By the preparation method of the QD@MOF of the skeleton structure of Technology for Heating Processing destruction MOF materials.
The content of the invention
In view of problem present in background technology, a purpose of the invention is to provide a kind of CdSe quantum dots and UIO-
The preparation method of 67 composites, it can avoid cap from sealing reagent to CdSe quantum dots and the catalytic of UIO-67 composites
Influence can be produced, while CdSe quantum dots and UIO-67 composites are prepared under normal temperature condition, can be avoided due to normal
Rule Technology for Heating Processing in temperature it is too high and produce without catalytic capability hexagonal phase CdSe quantum dot, while avoiding UIO-67 bones
Frame structure ruptures.
A kind of preparation method another object of the present invention is to provide CdSe quantum dots and UIO-67 composites, its
The UIO-67 materials of use possess specific surface area higher compared with other porous materials, and duct uniform, controllable is measured with CdSe
Son point can improve the decentralization of CdSe quantum dot when forming composite, and can control the chi of the CdSe quantum dot of generation
It is very little, and preparation process is simple, product can be easily separated, raw material availability it is high.
In order to achieve the above object, the invention provides a kind of CdSe quantum dots and the preparation side of UIO-67 composites
Method, it includes step：At normal temperatures and pressures, cadmium salt soln is distributed to inside UIO-67 in equal volume, by the use of inert gas as
Carrier gas is by H2Se gases are transferred in the container for filling UIO-67, terminate reaction, through ethanol washing, vacuum drying, obtain selenizing
Cadmium quantum dot and UIO-67 composites；Wherein, isometric dispersion refers to the cumulative volume and UIO-67 of the cadmium salt soln
The volume of the solvent for dissolving cadmium salt to be adsorbed is equal.
Relative to prior art, beneficial effects of the present invention are：
The preparation method of CdSe quantum dots of the invention and UIO-67 composites need not add cap to seal reagent, can be with
Avoid cap from sealing reagent and influence is produced on the catalytic performance of CdSe quantum dots and UIO-67 composites, while selenizing of the invention
Cadmium quantum dot and UIO-67 composites are prepared under normal temperature condition, can be avoided due to temperature mistake in normative heat treatment technique
High and generation does not have the hexagonal phase CdSe quantum dot of catalytic capability, while avoiding UIO-67 skeleton structures from rupturing.
In the preparation method of CdSe quantum dots of the invention and UIO-67 composites, the UIO-67 materials of use with
Other porous materials are compared, and possess specific surface area higher and duct uniform, controllable, and composite is being formed with CdSe quantum dot
When can improve the decentralization of CdSe quantum dot, and the CdSe quantum dot of controllable generation size, and preparation process is simple,
Product can be easily separated, raw material availability is high.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of the CdSe@UIO-67 composites of embodiment 1.
Fig. 2 is transmission electron microscope (TEM) figure of the CdSe@UIO-67 composites of embodiment 1.
Specific embodiment
The following detailed description of CdSe quantum dots of the invention and the preparation method of UIO-67 composites.
The preparation method of CdSe quantum dots and UIO-67 composites according to a first aspect of the present invention is illustrated first.
CdSe quantum dots and the preparation method of UIO-67 composites according to a first aspect of the present invention include step：
Under normal temperature and pressure, cadmium salt soln is distributed to inside UIO-67 in equal volume, by the use of inert gas as carrier gas by H2Se gases turn
Move in the container for filling UIO-67, terminate reaction, through ethanol washing, vacuum drying, obtain CdSe quantum dots and UIO-67
Composite (is abbreviated as CdSe@UIO-67)；Wherein, isometric dispersion refers to the cumulative volume and UIO- of the cadmium salt soln
The volume of 67 solvents for dissolving cadmium salt to be adsorbed is equal.
Due to the energy gap Eg=1.7eV of CdS semiconductor e, there is absorption to whole visible spectrum band, and urge in light
The aspects such as change, light degradation and photolysis water hydrogen have potential application value, in CdSe quantum dots of the invention and UIO-
In the preparation method of 67 composites, it is not necessary to add cap to seal reagent, can avoid cap seal reagent to CdSe quantum dots and
The catalytic performance of UIO-67 composites produces influence；Additionally, CdSe quantum dots of the invention and UIO-67 composites exist
Prepared under normal temperature condition, can avoid producing the hexagonal phase without catalytic capability because temperature is too high in normative heat treatment technique
CdSe quantum dot, while avoiding UIO-67 skeleton structures from rupturing.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, institute
CdSe quantum dot is Emission in Cubic in the CdSe quantum dots and UIO-67 composites of acquisition, active to visible ray, be can be used for
Photocatalysis, light degradation and photolysis water hydrogen.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, system
Extensively, raw material availability is high, preparation process is simple for the raw material sources of standby CdSe quantum dot, it is to avoid CdSe quantum dot is lost, and is reduced
Cost, and CdSe quantum dots and UIO-67 composites can regenerate.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, adopt
UIO-67 materials possess specific surface area higher and duct uniform, controllable compared with other porous materials, are measured with CdSe
Son point can improve the decentralization of CdSe quantum dot, and controllable CdSe quantum dot sub size when forming composite, and
Preparation process is simple, product can be easily separated, raw material availability is high, and the particle diameter of CdSe quantum dot is in 20nm or so.What is obtained
In CdSe@UIO-67 composites, the load capacity of CdSe quantum dot is higher, and the mass content of CdSe quantum dot may be up to 35%,
The specific surface area of CdSe@UIO-67 composites is 300m2/ g~1600m2/ g, place water in or air in several months structure not
Change.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, lead to
Cross isometric dispersion method and prepare CdSe quantum dots and UIO-67 composites, cumulative volume and the UIO-67 institutes of the cadmium salt soln
The volume of the solvent for dissolving cadmium salt that can be adsorbed is equal.If the cadmium salt soln for adding cumulative volume is larger and UIO-67
Quality it is relatively small, then can cause the most of residual of formed CdSe quantum dot in the solution, cause CdSe quantum dot
Raw material availability declines and the CdSe UIO-67 composites for obtaining can be made to be separated with the CdSe quantum dot being formed in solution
Become difficult；If the cumulative volume of the cadmium salt soln for adding is smaller and the relative mass of UIO-67 is larger, can cause in UIO-
The amount of the CdSe quantum dot of load is reduced in 67 skeletons, reduces the photocatalysis efficiency of CdSe@UIO-67 composites, and due to
The small volume of the cadmium salt soln of addition, causing the UIO-67 of part cannot effectively contact with cadmium salt soln so that CdSe quantum
Point can also influence the use of CdSe@UIO-67 composites in the intraskeletal skewness of UIO-67.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, cadmium
The cumulative volume of salting liquid is (1.4ml~1.6ml) with the mass ratio of UIO-67：1g.I.e. every gram UIO-67 can adsorb 1.4ml
~1.6ml is used to dissolve the solvent (such as water or alcohol) of cadmium salt, therefore, the UIO-67 of 1g is now often added, it is necessary to correspondence is added
Cadmium salt soln cumulative volume be 1.4ml~1.6ml.Preferably, the cumulative volume of cadmium salt soln is with the mass ratio of UIO-67
1.5ml：1g.The UIO-67 of 1g is preferably often added, it is necessary to the cumulative volume of the cadmium salt soln of correspondence addition is 1.5ml.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, use
Water or alcohol are may be selected from the solvent of dissolving cadmium salt, the alcohol is preferably ethanol.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, institute
Cadmium salt soln is stated for the cadmium salt aqueous solution or cadmium salt alcoholic solution.
It is excellent in the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites
Selection of land, the cadmium salt alcoholic solution is cadmium salt ethanol solution.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, institute
Cadmium salt is stated for cadmium nitrate or caddy.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, institute
The mass percent concentration for stating cadmium salt soln is 10%~40%.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites, institute
Inert gas is stated for nitrogen or argon gas.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites,
Under normal temperature and pressure, inside cadmium nitrate aqueous dispersion that 0.15ml mass percent concentrations are 10% to the UIO-67 of 100mg,
Then nitrogen buffer gas are by excessive H2Se gases are transferred in the container for filling UIO-67, after terminating reaction, washed through ethanol,
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites,
Under normal temperature and pressure, inside caddy aqueous dispersion that 0.15ml mass percent concentrations are 20% to the UIO-67 of 100mg,
Then nitrogen buffer gas are by excessive H2Se gases are transferred in the container for filling UIO-67, after terminating reaction, washed through ethanol,
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites.
In the preparation method of CdSe quantum dots described according to a first aspect of the present invention and UIO-67 composites,
Under normal temperature and pressure, the cadmium nitrate ethanol solution that 0.15ml mass percent concentrations are 40% is distributed in the UIO-67 of 100mg
Portion, then nitrogen buffer gas are by excessive H2Se gases are transferred in the container for filling UIO-67, after terminating reaction, are washed through ethanol
Wash, 60 DEG C be vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites.
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
Embodiment 1
At normal temperatures and pressures, by cadmium nitrate aqueous dispersion that 0.15ml mass percent concentrations are 10% to 100mg's
Ultrasound absorption 1h in UIO-67, then nitrogen buffer gas are by excessive H2Se gases are transferred to the closed container for filling UIO-67
In, treat that UIO-67 becomes kermesinus completely, terminate reaction, and the CdSe for removing and not combined with UIO-67 is washed with ethanol, then
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites, i.e. CdSe@UIO-67.
CdSe@UIO-67 composites are determined through X-ray polycrystalline diffraction (XRD), show the CdS-loaded e quantum dots of UIO-67
Structure does not change afterwards, and 2 θ show that the CdSe quantum dot of generation is Emission in Cubic (see figure in 25.3 °, 42 °, 49.7 ° of diffraction maximum
1).TEM (transmission electron microscope) result gives the surface topography (see Fig. 2) of CdSe@UIO-67 composites.CdSe quantum
The particle diameter of point is in 20nm or so.N under 77K2Isothermal adsorption test shows that the BET specific surface area of CdSe@UIO-67 composites is
1600m2/g.ICP-AES test structures show that CdSe quantum dot mass content in CdSe@UIO-67 composites is 10%.
Embodiment 2
At normal temperatures and pressures, by caddy aqueous dispersion that 0.15ml mass percent concentrations are 20% to 100mg's
Ultrasound absorption 1h in UIO-67, then nitrogen buffer gas are by excessive H2Se gases are transferred to the closed container for filling UIO-67
In, treat that UIO-67 becomes kermesinus completely, terminate reaction, and the CdSe for removing and not combined with UIO-67 is washed with ethanol, then
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites, i.e. CdSe@UIO-67.
CdSe@UIO-67 composites are through X-ray polycrystalline diffraction, and structure is similar to Example 1.N under 77K2Isothermal
Absorption test shows that the specific surface area of CdSe@UIO-67 composites is 934m2/g.ICP-AES test structures show, CdSe
Quantum dot mass content in CdSe@UIO-67 composites is 20%.The particle diameter of CdSe quantum dot is in 20nm or so.
Embodiment 3
At normal temperatures and pressures, the cadmium nitrate ethanol solution that 0.15ml mass percent concentrations are 40% is distributed to 100mg
UIO-67 in ultrasound absorption 1h, then nitrogen buffer gas are by excessive H2Se gases are transferred to the closed container for filling UIO-67
In, treat that UIO-67 becomes kermesinus completely, terminate reaction, and the CdSe for removing and not combined with UIO-67 is washed with ethanol, then
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites, i.e. CdSe@UIO-67.
CdSe@UIO-67 composites are through X-ray polycrystalline diffraction, and structure is similar to Example 1.N under 77K2Isothermal
Absorption test shows that the specific surface area of CdSe@UIO-67 composites is 300m2/g.ICP-AES test structures show, CdSe
Quantum dot mass content in CdSe@UIO-67 composites is 35%.The particle diameter of CdSe quantum dot is in 20nm or so.
Comparative example 1
At normal temperatures and pressures, the cadmium nitrate ethanol solution that 0.10ml mass percent concentrations are 40% is distributed to 100mg
UIO-67 in ultrasound absorption 1h, then nitrogen buffer gas are by excessive H2Se gases are transferred to the closed container for filling UIO-67
In, treat that UIO-67 becomes kermesinus completely, terminate reaction, and the CdSe for removing and not combined with UIO-67 is washed with ethanol, then
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites, i.e. CdSe@UIO-67.
CdSe@UIO-67 composites are through X-ray polycrystalline diffraction, and structure is similar to Example 1.N under 77K2Isothermal
Absorption test shows that the specific surface area of CdSe@UIO-67 composites is 670m2/g.ICP-AES test structures show, CdSe
Quantum dot mass content in CdSe@UIO-67 composites is 23%.The particle diameter of CdSe quantum dot is in 20nm or so.
Due to the small volume of cadmium nitrate ethanol solution, it is impossible to complete wetting UIO-67, cause to be born in UIO-67 skeletons
The amount of the CdSe quantum dot of load is less, reduces the catalytic efficiency of CdSe@UIO-67 composites.
Comparative example 2
At normal temperatures and pressures, the cadmium nitrate ethanol solution that 10ml mass percent concentrations are 40% is distributed to 100mg's
Ultrasound absorption 1h in UIO-67, then nitrogen buffer gas are by excessive H2Se gases are transferred to the closed container for filling UIO-67
In, treat that UIO-67 becomes kermesinus completely, terminate reaction, and the CdSe for removing and not combined with UIO-67 is washed with ethanol, then
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites, i.e. CdSe@UIO-67.
CdSe@UIO-67 composites are through X-ray polycrystalline diffraction, and structure is similar to Example 1.N under 77K2Isothermal
Absorption test shows that the specific surface area of CdSe@UIO-67 composites is 230m2/g.ICP-AES test structures show, CdSe
Quantum dot mass content in CdSe@UIO-67 composites is 33.5%.The particle diameter of CdSe quantum dot is in 20nm or so.
But because the volume of cadmium nitrate ethanol solution is larger, then can cause the most of residual of formed CdSe quantum dot
In the solution, the raw material availability of CdSe quantum dot is caused to decline, the waste for causing cadmium nitrate ethanol solution unnecessary, and can make
The CdSe UIO-67 composites for obtaining are separated with the CdSe quantum dot for being formed in the solution becomes difficult.
Claims (10)
1. the preparation method of a kind of CdSe quantum dots and UIO-67 composites, it is characterised in that including step：
At normal temperatures and pressures, cadmium salt soln is distributed to inside UIO-67 in equal volume, by the use of inert gas as carrier gas by H2Se gas
Body is transferred in the container for filling UIO-67, terminate reaction, through ethanol washing, vacuum drying, obtain CdSe quantum dots and
UIO-67 composites；
Wherein, isometric dispersion refer to the cadmium salt soln cumulative volume and UIO-67 to be adsorbed for dissolving cadmium
The volume of the solvent of salt is equal.
2. the preparation method of CdSe quantum dots according to claim 1 and UIO-67 composites, it is characterised in that cadmium
The cumulative volume of salting liquid is (1.4ml~1.6ml) with the mass ratio of UIO-67：1g, it is preferable that the cumulative volume of cadmium salt soln with
The mass ratio of UIO-67 is 1.5ml：1g.
3. the preparation method of CdSe quantum dots according to claim 1 and UIO-67 composites, it is characterised in that use
Water or alcohol are selected from the solvent of dissolving cadmium salt, the cadmium salt soln is the cadmium salt aqueous solution or cadmium salt alcoholic solution.
4. the preparation method of CdSe quantum dots according to claim 3 and UIO-67 composites, it is characterised in that use
Ethanol is selected from the solvent of dissolving cadmium salt, the cadmium salt alcoholic solution is cadmium salt ethanol solution.
5. the preparation method of CdSe quantum dots according to claim 1 and UIO-67 composites, it is characterised in that institute
Cadmium salt is stated for cadmium nitrate or caddy.
6. the preparation method of CdSe quantum dots according to claim 1 and UIO-67 composites, it is characterised in that institute
The mass percent concentration for stating cadmium salt soln is 10%~40%.
7. the preparation method of CdSe quantum dots according to claim 1 and UIO-67 composites, it is characterised in that institute
Inert gas is stated for nitrogen or argon gas.
8. the preparation method of CdSe quantum dots according to claim 2 and UIO-67 composites, it is characterised in that
Under normal temperature and pressure, inside cadmium nitrate aqueous dispersion that 0.15ml mass percent concentrations are 10% to the UIO-67 of 100mg,
Then nitrogen buffer gas are by excessive H2Se gases are transferred in the container for filling UIO-67, after terminating reaction, washed through ethanol,
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites.
9. the preparation method of CdSe quantum dots according to claim 2 and UIO-67 composites, it is characterised in that
Under normal temperature and pressure, inside caddy aqueous dispersion that 0.15ml mass percent concentrations are 20% to the UIO-67 of 100mg,
Then nitrogen buffer gas are by excessive H2Se gases are transferred in the container for filling UIO-67, after terminating reaction, washed through ethanol,
60 DEG C are vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites.
10. the preparation method of CdSe quantum dots according to claim 2 and UIO-67 composites, it is characterised in that
At normal temperatures and pressures, the cadmium nitrate ethanol solution that 0.15ml mass percent concentrations are 40% is distributed to the UIO-67 of 100mg
Inside, then nitrogen buffer gas are by excessive H2Se gases are transferred in the container for filling UIO-67, after terminating reaction, through ethanol
Washing, 60 DEG C be vacuum dried 6 hours, obtain CdSe quantum dots and UIO-67 composites.
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