CN105664955B - A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc - Google Patents
A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims abstract description 18
- ATSGLBOJGVTHHC-UHFFFAOYSA-N bis(ethane-1,2-diamine)copper(2+) Chemical compound [Cu+2].NCCN.NCCN ATSGLBOJGVTHHC-UHFFFAOYSA-N 0.000 claims abstract description 17
- NEUOBESLMIKJSB-UHFFFAOYSA-J tetrasodium;tetraacetate Chemical compound [Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O NEUOBESLMIKJSB-UHFFFAOYSA-J 0.000 claims abstract description 17
- 238000000502 dialysis Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- ZJKUNLIROZVUOJ-UHFFFAOYSA-N [Na].[Zn].C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(CN)N Chemical compound [Na].[Zn].C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(CN)N ZJKUNLIROZVUOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004925 dihydropyridyl group Chemical group N1(CC=CC=C1)* 0.000 abstract 1
- AXQVDHLAIKEGQG-UHFFFAOYSA-K [Na+].[Zn+2].C(C)(=O)[O-].C(C)(=O)O.C(C)(=O)[O-].C(C)(=O)[O-].C(CN)N Chemical compound [Na+].[Zn+2].C(C)(=O)[O-].C(C)(=O)O.C(C)(=O)[O-].C(C)(=O)[O-].C(CN)N AXQVDHLAIKEGQG-UHFFFAOYSA-K 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002096 quantum dot Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical class C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 150000004699 copper complex Chemical class 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 150000004753 Schiff bases Chemical group 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- -1 cupric ethylene diamine tetraacetate sodium salts Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
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Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention relates to a kind of preparation method of the metal co-doped carbon quantum dot of copper zinc, including step are as follows：(1) after mixing cupric ethylene diamine tetraacetate sodium and ethylenediamine tetra-acetic acid zinc sodium, under oxygen free condition, 250 450 DEG C, the 5h of isothermal reaction 1 are warming up to, then Temperature fall；(2) it is step (1) reacted material is soluble in water, it is uniformly dispersed, then filters, removes the material that particle diameter is more than 0.22 μm；(3) dialysed after the solution that step (2) obtains is concentrated, remove small molecular weight impurity, then the solution after dialysis is evaporated, produced.The present invention is combined copper, zinc with carbon quantum dot, acted synergistically by both, it significantly can effectively strengthen visible light-responded ability and electric transmission efficiency, from catalysis 1, from the point of view of the effect of 4 dihydropyridines, hybrid metal doping carbon quantum dot catalytic effect than single metal carbon quantum dot excellent catalytic effect.
Description
Technical field
The present invention relates to a kind of preparation method of the metal co-doped carbon quantum dot of copper zinc, belong to technology of quantum dots field.
Background technology
Using the sunshine of rich reserves as energy source, photocatalysis oxidation reaction obtains vast grind with its environmental and economy
Study carefully the favor of personnel.Luminous energy be unable to do without the excellent photosensitive nanoparticle material of catalytic activity with chemical energy effectively conversion.Therefore, led at this
Domain, the cheap material of cost will gradually substitute the catalyst based on noble metal.Carbon quantum dot has good water solubility, low
Poison, the advantages that good biocompatibility, and have the characteristics that visible light-responded scope is wide, its class graphene-structured, be advantageous to electronics
Transfer transmission；Therefore carbon quantum dot has a wide range of applications in light-catalyzed reaction, and the application process of carbon quantum dot is mostly first
It is compound with other materials, be so advantageous to improve the performance of light-catalyzed reaction.
At present, carbon quantum dot composite generally first prepares metal nanoparticle and carbon quantum dot respectively, then incite somebody to action the two
It is compound.But both composites for preparing of this method skewness, interaction force is weaker, certain defect be present.
Chinese patent document CN104759283A (application numbers：201510101628.5) disclose and a kind of be based on copper complex
Carbon quantum dot and preparation method thereof, be raw material using the cupric ethylene diamine tetraacetate sodium salt with saturation Schiff base structure, by copper
Complex and with class graphene-structured carbon quantum dot it is compound, using thermal polymerization method prepare the carbon quantum dot based on copper complex,
Improve the electron transfer capacity of such sensitising agent.Although should be based on copper complex formazan carbon quantum dot in photocatalysis 1,4- dihydropyridines
In reaction, catalytic efficiency improves, and still, photocatalysis efficiency still has to be strengthened.
The content of the invention
For being not so good as prior art, the present invention provides a kind of preparation method of the metal co-doped carbon quantum dot of copper zinc,
Using cupric ethylene diamine tetraacetate sodium salt and ethylenediamine tetra-acetic acid zinc sodium salt mixt as presoma, react, dissolve by hot polymerization, ultrasound
Concussion, centrifuge, concentrate dialysis and be evaporated obtained.
Technical scheme is as follows：
A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc, including step are as follows：
(1) after cupric ethylene diamine tetraacetate sodium and ethylenediamine tetra-acetic acid zinc sodium being mixed, under oxygen free condition, be warming up to 250 DEG C-
450 DEG C, isothermal reaction 1-5h, then Temperature fall；
(2) it is step (1) reacted material is soluble in water, it is uniformly dispersed, then filters, removes particle diameter and be more than 0.22 μm
Material；
(3) dialysed after the solution that step (2) obtains is concentrated, remove small molecular weight impurity, then steam the solution after dialysis
It is dry, obtain the metal co-doped carbon quantum dot of solid copper zinc.
, according to the invention it is preferred to, the mass ratio of cupric ethylene diamine tetraacetate sodium and ethylenediamine tetra-acetic acid zinc sodium in step (1)
For (0.3-1)：1, further preferred (0.8-1)：1, most preferably 1:1；
Preferably, the speed of heating is 1-20 DEG C/min；Make raw material in pre-heat phase not because of temperature under the heating rate
Heat up too fast, cause raw material drain evaporation, ensure that yield, also will not be because of the too low influence production efficiency of heating-up temperature；
Preferably, reaction temperature is 300-400 DEG C；The generation of carbon quantum dot is ensure that under the reaction temperature, will not be in mistake
At high temperature, strong hot polymerization reaction occurs, the matter dimensions of generation are excessive, so that reducing the yield of carbon quantum dot；Together
When ensure carbon nano-quantum point in copper, Zn complex content.
, according to the invention it is preferred to, finely dispersed mode is ultrasonic disperse in step (2), and the frequency of ultrasonic disperse is
80-150Hz；
Preferably, the mode of filtering is to remove material of the particle diameter more than 0.22 μm with 0.22 μm of filter membrane.
, according to the invention it is preferred to, the dialysis described in step (3) is the bag filter with 3000-4000D, and dialysis removes
Small molecular weight impurity；
Preferably, the temperature being evaporated is 50-70 DEG C.
In the present invention, copper, zinc are combined with carbon quantum dot, is acted synergistically, can effectively strengthened visible light-responded by both
Ability and electric transmission efficiency, and then extend its application in photocatalysis oxidation reaction.The present invention, which uses, has class Schiff base
The cupric ethylene diamine tetraacetate sodium salt and ethylenediamine tetra-acetic acid zinc sodium salt of saturated structures are organic carbon source, are reacted by high temperature hot polymerization
Prepare good water solubility, uniform particle diameter, fluorescence property stabilization, the hybrid metal of wide, the high electric transmission efficiency of visible light-responded scope
The carbon quantum dot of doping, for photochemical catalytic oxidation Isosorbide-5-Nitrae-dihydropyridine, good effect is achieved, 93.93% can be will be up to
Isosorbide-5-Nitrae-dihydropyridine is converted into pyridine derivatives, and realizes and reacted in aqueous, and accessory substance is exactly water and oxygen
Gas, green photochemical requirement is reached.
The excellent effect of the present invention is as follows：
1st, the present invention is combined copper, zinc with carbon quantum dot, is acted synergistically by both, significantly can effectively strengthen visible ray sound
Should be able to power and electric transmission efficiency, from the point of view of the effect of catalysis Isosorbide-5-Nitrae-dihydropyridine, the carbon quantum dot of hybrid metal doping is urged
Change excellent catalytic effect of the effect than single metal carbon quantum dot.
2nd, copper zinc hybrid metal doping carbon quantum dot of the present invention has good in the experiment of photocatalysis 1,4- dihydropyridines
Catalytic effect, 93.93% Isosorbide-5-Nitrae-dihydropyridine can be converted into pyridine derivatives, and realize and carry out in aqueous
Reaction, accessory substance is only water and oxygen, has reached green photochemical requirement.
3rd, present invention optimization carbon source structure, the carbon quantum dot that one-step method directly generates copper, zinc hybrid metal adulterates, section are utilized
Process is saved, improves product stability.
Brief description of the drawings
Fig. 1 is transmission electron microscope (TEM) figure (a) and particle diameter of the metal co-doped carbon quantum dot of copper zinc made from embodiment 1
Distribution map (b)；
Fig. 2 is fluorescent emission of the metal co-doped carbon quantum dot of copper zinc under different excitation wavelengths made from embodiment 1
Spectrogram；
Fig. 3 is the mechanism figure that the metal co-doped carbon quantum dot of copper zinc of the present invention is catalyzed 1,4- dihydropyridines；Wherein, CQDs
For the metal co-doped carbon quantum dot of copper zinc, Isosorbide-5-Nitrae-DHP is Isosorbide-5-Nitrae-dihydropyridine；
Fig. 4 is Cu in the metal co-doped carbon quantum dot of copper zinc made from embodiment 12+Electron spin resonance (ESR) figure
And Zn (a)1+ESR figure (b)；
Fig. 5 is Cu in the metal co-doped carbon quantum dot of copper zinc after addition 1,4- dihydropyridines in test example 22+ESR figure
And Zn (a)1+ESR figure (b)；
Fig. 6 is the uv absorption spectra of the metal co-doped carbon quantum dot of copper zinc made from embodiment 1 in test example 1；
Fig. 7 is the catalytic curve figure that quantum dot is catalyzed 1,4- dihydropyridines in test example 2.
Embodiment
Below by specific embodiment and with reference to accompanying drawing, the present invention will be further described, but not limited to this.
Embodiment 1
A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc, including step are as follows：
(1) cupric ethylene diamine tetraacetate sodium salt and ethylenediamine tetra-acetic acid zinc sodium salt common 3.0g (cupric ethylene diamine tetraacetate sodium are weighed
The mass ratio of salt and ethylenediamine tetra-acetic acid zinc sodium salt is 1:1) uniformly tile into quartz boat, quartz boat is then put into tubular type
In heating furnace.N2Bubbling 30min, drive away the oxygen in pipe.After 30min, start heater, with the 5 DEG C/min rate of heat addition
Carry out heating heating.After being warming up to 350 DEG C, constant temperature 5h is maintained, then Temperature fall, takes out after being down to room temperature.
(2) step (1) reacted sample is dissolved into 100mL water, carried out in 100Hz ultrasonic vibration instrument
20min ultrasonic vibration effect, is completely dissolved part soluble in water.Then filtration treatment is carried out with 0.22 μm of filter membrane,
Remove the material more than 0.22 μm.
(3) after the liquid concentration for obtaining step (2), dialysis treatment is carried out in 3500D bag filter.Removed by dialysis
The partial salts and small molecular weight impurity contained in carbon elimination quantum dot solution.Solution after dialysis is evaporated in 50 DEG C of baking oven, is obtained
The carbon quantum dot metal co-doped to solid copper zinc.
Shown in transmission electron microscope picture such as Fig. 1 (a) of the metal co-doped carbon quantum dot of copper zinc made from the present embodiment, particle diameter point
Shown in Butut such as Fig. 1 (b).As shown in Figure 1, the carbon quantum dot of copper zinc hybrid metal doping, size uniformity, average-size are
2.2nm, it is observed that the spacing of lattice of carbon quantum dot, about 0.2nm, this and graphene under high power transmission electron microscope
(002) diffraction crystal face matches.
Cu in the metal co-doped carbon quantum dot of copper zinc made from the present embodiment2+Electron spin resonance (ESR) figure such as Fig. 4
(a) shown in, Zn1+ESR figures as shown in Fig. 4 (b).As shown in Figure 4, copper zinc hybrid metal doping carbon quantum dot by illumination it
Afterwards, Cu2+And Zn1+Signal decline because Cu2+It is reduced to Cu1+, it is difficult to be oxidized to Cu0, and Zn1+It is oxidized to
Zn2+。
Embodiment 2
A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc, including step are as follows：
(1) cupric ethylene diamine tetraacetate sodium salt and ethylenediamine tetra-acetic acid zinc sodium salt common 3.0g (cupric ethylene diamine tetraacetate sodium are weighed
The mass ratio of salt and ethylenediamine tetra-acetic acid zinc sodium salt is 0.5:1) uniformly tile into quartz boat, quartz boat is then put into pipe
In formula heating furnace.N2Bubbling 30min, drive away the oxygen in pipe.After 30min, start heater, with 1 DEG C/min heating speed
Rate carries out heating heating.After being warming up to 250 DEG C, constant temperature 2h is maintained, then Temperature fall, takes out after being down to room temperature.
(2) step (1) reacted sample is dissolved into 100mL water, 20min is carried out in 80Hz ultrasonic vibration instrument
Ultrasonic vibration effect, be completely dissolved part soluble in water.Then filtration treatment is carried out with 0.22 μm of filter membrane, removed big
In 0.22 μm of material.
(3) after the liquid concentration for obtaining step (2), dialysis treatment is carried out in 3000D bag filter.Removed by dialysis
The partial salts and small molecular weight impurity contained in carbon elimination quantum dot solution.Solution after dialysis is evaporated in 50 DEG C of baking oven, is obtained
The carbon quantum dot metal co-doped to solid copper zinc.
Embodiment 3
A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc, including step are as follows：
(1) cupric ethylene diamine tetraacetate sodium salt and ethylenediamine tetra-acetic acid zinc sodium salt common 3.0g (cupric ethylene diamine tetraacetate sodium are weighed
The mass ratio of salt and ethylenediamine tetra-acetic acid zinc sodium salt is 0.8:1) uniformly tile into quartz boat, quartz boat is then put into pipe
In formula heating furnace.N2Bubbling 30min, drive away the oxygen in pipe.After 30min, start heater, with 10 DEG C/min heating speed
Rate carries out heating heating.After being warming up to 400 DEG C, constant temperature 2h is maintained, then Temperature fall, takes out after being down to room temperature.
(2) step (1) reacted sample is dissolved into 100mL water, carried out in 120Hz ultrasonic vibration instrument
20min ultrasonic vibration effect, is completely dissolved part soluble in water.Then filtration treatment is carried out with 0.22 μm of filter membrane,
Remove the material more than 0.22 μm.
(3) after the liquid concentration for obtaining step (2), dialysis treatment is carried out in 4000D bag filter.Removed by dialysis
The partial salts and small molecular weight impurity contained in carbon elimination quantum dot solution.Solution after dialysis is evaporated in 70 DEG C of baking oven, is obtained
The carbon quantum dot metal co-doped to solid copper zinc.
Comparative example 1
The preparation method of the metal co-doped carbon quantum dot of copper zinc as described in Example 1, unlike：
The mass ratio of cupric ethylene diamine tetraacetate sodium salt and ethylenediamine tetra-acetic acid zinc sodium salt is 2 in step (1):1.
Comparative example 2
The preparation method of the metal co-doped carbon quantum dot of copper zinc as described in Example 1, unlike：
3g ethylenediamine tetra-acetic acid zinc sodium salts are used only in step (1).
Comparative example 3
The preparation method of the metal co-doped carbon quantum dot of copper zinc as described in Example 1, unlike：
3g disodium edtas are used only in step (1).
Comparative example 4
The preparation method of the metal co-doped carbon quantum dot of copper zinc as described in Example 1, unlike：
3g cupric ethylene diamine tetraacetate sodium salts are used only in step (1).
Test example 1
The uv absorption spectra of the metal co-doped carbon quantum dot of copper zinc made from testing example 1,2 and comparative example 1,
As shown in fig. 6, it will be appreciated from fig. 6 that copper zinc metal mixed doping carbon quantum dot have very wide absworption peak from 300nm to 600nm, when
Copper zinc ratio is 1:When 1, absorption is most strong, is mainly due to π → π * transition of graphite-structure.
Test example 2
Quantum dot made from embodiment 1-3 and comparative example 1-4 is used for photocatalysis Isosorbide-5-Nitrae-dihydropyridine experiment, step is such as
Under：
Take 3mg solid sample to be dissolved into the mixed solution of 20mL water/ethanol, by 90min illumination, test substrate
By the efficiency of catalysis oxidation, as a result as shown in table 1.
By Cu after the metal co-doped carbon quantum dot addition 1,4- dihydropyridines of copper zinc made from embodiment 12+ESR figure such as
Shown in Fig. 5 (a), Zn1+ESR figures as shown in Fig. 5 (b)；As shown in Figure 5, after illumination, Zn1+Signal increase, Cu2+'s
Signal is held essentially constant.It is by Zn2+Reacted with Isosorbide-5-Nitrae-dihydropyridine, generate Zn1+It is caused.
Table 1
As shown in Table 1, the obvious high catalytic efficiencies than comparative example 1-4 of embodiment 1-3.
The data of quantum dot catalysis Isosorbide-5-Nitrae-dihydropyridine made from embodiment 1-2 and comparative example 1 are drawn into curve, such as Fig. 7
It is shown.As shown in Figure 7, embodiment 1-2 is substantially than the high catalytic efficiency of comparative example 1.
Claims (9)
1. a kind of preparation method of the metal co-doped carbon quantum dot of copper zinc, including step are as follows：
（1）After cupric ethylene diamine tetraacetate sodium and ethylenediamine tetra-acetic acid zinc sodium are mixed, under oxygen free condition, 250 °C 450 is warming up to
°C, isothermal reaction 1-5 h, then Temperature fall；
The mass ratio of cupric ethylene diamine tetraacetate sodium and ethylenediamine tetra-acetic acid zinc sodium is（0.3-1）：1；
（2）By step（1）Reacted material is soluble in water, is uniformly dispersed, and then filters, and removes particle diameter and is more than 0.22 μm
Material；
（3）By step（2）Dialysed after obtained solution concentration, remove small molecular weight impurity, then the solution after dialysis is evaporated, obtained
The metal co-doped carbon quantum dot of solid copper zinc.
2. the preparation method of the metal co-doped carbon quantum dot of copper zinc according to claim 1, it is characterised in that step
（1）The mass ratio of middle cupric ethylene diamine tetraacetate sodium and ethylenediamine tetra-acetic acid zinc sodium is（0.8 -1）：1.
3. the preparation method of the metal co-doped carbon quantum dot of copper zinc according to claim 1, it is characterised in that step
（1）The mass ratio of middle cupric ethylene diamine tetraacetate sodium and ethylenediamine tetra-acetic acid zinc sodium is 1：1.
4. the preparation method of the metal co-doped carbon quantum dot of copper zinc according to claim 1, it is characterised in that step
（1）The speed of middle heating is 1 20 °C/min.
5. the preparation method of the metal co-doped carbon quantum dot of copper zinc according to claim 1, it is characterised in that step
（1）Middle reaction temperature is 300 400 °C.
6. the preparation method of the metal co-doped carbon quantum dot of copper zinc according to claim 1, it is characterised in that step
（2）In finely dispersed mode be ultrasonic disperse, the frequency of ultrasonic disperse is 80-150 Hz.
7. the preparation method of the metal co-doped carbon quantum dot of copper zinc according to claim 1, it is characterised in that step
（2）The mode of middle filtering is to remove material of the particle diameter more than 0.22 μm with 0.22 μm of filter membrane.
8. the preparation method of the metal co-doped carbon quantum dot of copper zinc according to claim 1, it is characterised in that step
（3）Described in dialysis be bag filter with 3000-4000 D.
9. the preparation method of the metal co-doped carbon quantum dot of copper zinc according to claim 1, it is characterised in that step
（3）Described in the temperature that is evaporated be 50-70 °C.
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