CN105879916A - Preparation method of perylene diimide functionalization copper oxide nanocomposite - Google Patents
Preparation method of perylene diimide functionalization copper oxide nanocomposite Download PDFInfo
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- CN105879916A CN105879916A CN201610373657.1A CN201610373657A CN105879916A CN 105879916 A CN105879916 A CN 105879916A CN 201610373657 A CN201610373657 A CN 201610373657A CN 105879916 A CN105879916 A CN 105879916A
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- imidodicarbonic diamide
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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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
Abstract
The invention discloses a preparation method of a perylene diimide functionalization copper oxide nanocomposite. The method comprises the following steps that a water-soluble copper salt and sodium dodecyl benzene sulfonate are dissolved into deionized water, a sodium hydroxide solution is added dropwisely while stirring is performed, and stirring continues to be performed for 0.5 h; then, indoor temperature aging is performed for 4 h to obtain a suspension; drying is performed for 6 h, and centrifuging, washing, drying and calcination are performed to obtain a copper oxide nanoribbon; the synthesized material is added into an N,N-dimethyl formamide solution with dissolved perylene diimide; after ultrasonography is performed, centrifuging, washing and drying are performed to obtain a copper oxide-perylene diimide nanocomposite. According to the method, the perylene diimide functionalization copper oxide nanocomposite is synthesized for the first time, the method has the advantages of being simple in preparation technology, low in cost, mild in reaction condition and the like, and the nanocomposite obtained through the method has the advantages of being high in purity, small in size, good in catalytic activity and the like.
Description
Technical field
The present invention relates to the preparation method of cupric oxide (PDI-CuO) nano composite material of a kind of imidodicarbonic diamide functionalization, belong to the preparing technical field of nano composite material.
Background technology
Transition metal is due to special valency electricity structure so that it is have multiple valence state.The transition metal oxide that transition metal is corresponding is also important functional material, has a wide range of applications.Wherein cupric oxide (CuO) has narrower energy gap about 1.2 eV, is a kind of typical p-type semiconductor.After the size of copper oxide particle reaches nanoscale, there has been the distinctive quantum size effect of nano material, skin effect and macro quanta tunnel effect, as shown high catalysis activity as catalysis material, apply on a sensor as light-sensitive material, also can be applied at the aspect such as thermal conducting material and superconductor.
The shortcoming easily adsorb yet with single nano material, easily reunited, causes its chemism position to be reduced, thus causes the reduction of its activity.In order to overcome this defect, sight has been turned in the modification to metal oxide by researchers.
Imidodicarbonic diamide (PDI) is a kind of typical N-shaped organic semiconducting materials, it it is an electron deficient system, there is special condensed cyclic structure, the strongest absorption is had in visible region, and have the highest light, heat endurance, it is a kind of optical physics with uniqueness and the organic semiconducting materials of thermochemical property, is widely used in fields such as electroluminescent material, solar energy conversion, biological fluorescent labelings.
Summary of the invention
For the disadvantages mentioned above existing for single copper oxide nano material, the invention provides the cupric oxide nano composite process of a kind of two-step method synthesis imidodicarbonic diamide functionalization.
The adopted technical solution is that:
The preparation method of the cupric oxide nano composite of a kind of imidodicarbonic diamide functionalization, comprises the following steps:
(1) choosing imidodicarbonic diamide, DMF, water-soluble mantoquita, neopelex and NaOH are raw material；
(2) copper chloride and neopelex are dissolved in deionized water, and under agitation drip sodium hydroxide solution, obtain light blue solution；
(3), after aged at room temperature, suspension is obtained；
(4) suspension is transferred in reactor 100 DEG C be dried, by centrifugation, washs, be dried and calcining, prepare Copper oxide nano-belt；
(5) prepared cupric oxide is joined dissolve imidodicarbonic diamide DMF solution in, ultrasonic 0.5 h, by centrifugation, wash, be dried, prepare imidodicarbonic diamide functionalization cupric oxide nano composite.
In step (1): described water-soluble mantoquita is water miscible copper chloride, copper nitrate, copper acetate；Described water-soluble mantoquita is 1:40～1:60 with the mol ratio of NaOH.
In step (2): described concentration of sodium hydroxide solution is 4～6 mol/L.
In step (3): described ageing time is 4～5 h.
In step (4): described baking temperature is 100～110 DEG C；Described calcining heat is 350 DEG C.
In step (5): the concentration of described imidodicarbonic diamide is 1 g/L～3 g/L.
The method have the benefit that:
The present invention uses imidodicarbonic diamide to modify, and the copper oxide nano particle of the imidodicarbonic diamide functionalization prepared has the advantages such as purity is high, size is little, catalysis activity is good, has preferable class peroxidase activity；Additionally the present invention uses two-step method to prepare product, the advantage such as the method has that preparation technology is simple, easy and simple to handle, low cost, reaction time are short and reaction condition is gentle.As colorimetric bio sensor, there is when detecting hydrogen peroxide the features such as simplicity, stable, highly sensitive, selectivity is the strongest using it.
Accompanying drawing explanation
The invention will be further described with detailed description of the invention below in conjunction with the accompanying drawings:
Fig. 1 is copper oxide nano particle X-ray diffractogram；
Fig. 2 is the copper oxide nano particle X-ray diffractogram of the imidodicarbonic diamide functionalization that embodiment 1 prepares, and wherein, curve A is the X-ray diffractogram of cupric oxide, and curve B is the X-ray diffractogram of the copper oxide nano material of the imidodicarbonic diamide functionalization that embodiment 1 prepares；
Fig. 3 is the transmission electron microscope picture of the copper oxide nano particle of the imidodicarbonic diamide functionalization that embodiment 1 prepares；
Fig. 4 is the ultraviolet-visible absorption spectroscopy figure of differential responses system.
Detailed description of the invention
Embodiment 1
1. by 0.171 g copper chloride (CuCl2∙H2O) it is dissolved in 10 mL deionized waters with 0.348 g neopelex.Under stirring condition, the sodium hydroxide solution of dropping 10mL 5M, continues stirring 0.5 h；Then aged at room temperature 4 h obtains suspension.This system is proceeded in 25 mL reactors, 100 DEG C of reaction 6 h.Through being centrifuged, wash, be dried and calcining, obtain Copper oxide nano-belt.2. weigh 2.5 mg imidodicarbonic diamide and be completely dissolved in 2.5mL N, dinethylformamide is formed solution A, the cupric oxide of above-mentioned synthesis is added in A, ultrasonic 0.5 h, 3 times are respectively washed with deionized water and ethanol after Li Xin, and at 60 DEG C, it is dried 4 h, obtain the cupric oxide nano composite of imidodicarbonic diamide functionalization.
Testing products obtained therefrom, result is as shown in Figure 1, Figure 2, Figure 3 shows.From figure 1 it appears that the peak in spectrogram both corresponds to the diffraction maximum of CuO, consistent with the standard card (JCPDS48-158) of the CuO of the report of document before, and there is no other miscellaneous peaks, thus prove that products obtained therefrom is pure CuO；In Fig. 2 compared with A with B, the copper oxide nano material of imidodicarbonic diamide functionalization somewhat weakens on diffraction peak intensity, and peak position is similar with the A of Fig. 2, it was demonstrated that imidodicarbonic diamide is the most successfully combined, and the not change of the crystal formation of functionalization rear oxidation copper nano-particle, size somewhat becomes big；It can be seen that the copper oxide nano material of imidodicarbonic diamide functionalization presents banding from Fig. 3 transmission electron microscope picture.
Embodiment 2
1. by 0.1425 g copper chloride (CuCl2∙H2O) it is dissolved in 10 mL deionized waters with 0.348 g neopelex.Under stirring condition, the sodium hydroxide solution of dropping 10mL 5M, continues stirring 0.5 h；Then aged at room temperature 4 h obtains suspension.This system is proceeded in 25 mL reactors, 100 DEG C of reaction 6 h.Through being centrifuged, wash, be dried and calcining, obtain Copper oxide nano-belt.2. weigh 2.5 mg imidodicarbonic diamide and be completely dissolved in 2.5mL N, dinethylformamide is formed solution A, the cupric oxide of above-mentioned synthesis is added in A, ultrasonic 0.5 h, 3 times are respectively washed with deionized water and ethanol after Li Xin, and at 60 DEG C, it is dried 4 h, obtain the cupric oxide nano composite of imidodicarbonic diamide functionalization.
Embodiment 3
1. by 0.21375 g copper chloride (CuCl2∙H2O) it is dissolved in 10 mL deionized waters with 0.348 g neopelex.Under stirring condition, the sodium hydroxide solution of dropping 10mL 5M, continues stirring 0.5 h；Then aged at room temperature 4 h obtains suspension.This system is proceeded in 25 mL reactors, 100 DEG C of reaction 6h.Through being centrifuged, wash, be dried and calcining, obtain Copper oxide nano-belt.2. weigh 2.5 mg imidodicarbonic diamide and be completely dissolved in 2.5mL N, dinethylformamide is formed solution A, the cupric oxide of above-mentioned synthesis is added in A, ultrasonic 0.5 h, 3 times are respectively washed with deionized water and ethanol after Li Xin, and at 60 DEG C, it is dried 4 h, obtain the cupric oxide nano composite of imidodicarbonic diamide functionalization.
On the basis of above-described embodiment, in addition it is also necessary to the present invention is carried out as described below.
In above-described embodiment 1～3, raw materials used imidodicarbonic diamide is oneself synthesis, and it is pure that other raw materials used are analysis.
Analogue enztme activity colorimetric is tested:
1. prepare the sodium acetate-hac buffer A of pH=3.8；
Copper oxide nano particle 3 mg the most accurately weighing the imidodicarbonic diamide functionalization prepared by embodiment 1 is dissolved in 10 mL redistilled waters, makes it be uniformly dispersed, obtained solution B under ultrasound condition；
The most accurately weigh copper oxide nano particle 3 mg prepared by embodiment 1 to be dissolved in 10 mL redistilled waters, make it be uniformly dispersed under ultrasound condition, obtained solution C；
4. measure 240 μ L 30% hydrogen peroxide (H2O2) constant volume to 10 mL, be configured to the solution D of 0.25 mol/L；
5. weigh the TMB(3,3', 5 of 6 mg, 5'-tetramethyl benzidine) it is dissolved in 10 mL redistilled waters, it is formulated as the solution E that molar concentration is 2.0 mmol/L；
A: measure 1400 μ L A+200 μ L B+200 μ L D+200 μ L E with pipettor and be placed in the cuvette of 5 mL；
B: measure 1400 μ L A+200 μ L C+200 μ L D+200 μ L E with pipettor and be placed in the cuvette of 5 mL；
C: measure 1600 μ L A+200 μ L B+200 μ L E with pipettor and be placed in the cuvette of 5 mL；
D: measure 1600 μ L A+200 μ L D+200 μ L E with pipettor and be placed in the cuvette of 5 mL；
E: measure 1800 μ L A+ 200 μ L E with pipettor and be placed in the cuvette of 5 mL；
At room temperature reacting, observe and find: after 40 seconds, the liquid in a cuvette starts to show slight blueness, after one minute, the liquid in b cuvette just can manifest slight color change；After ten a few minutes, in the cuvette of d, e, liquid becomes blue in succession, and the color in c is not changed in all the time.
Interpretation of result: H2O2TMB can be aoxidized and produce significantly blue, by above-mentioned experimental observations it can be seen that compared to b adds cupric oxide, after a adds the copper oxide nano particle of imidodicarbonic diamide functionalization, H2O2Change faster with the reaction color of TMB, illustrate that the copper oxide nano particle of the imidodicarbonic diamide functionalization prepared by the present invention serves fine catalytic effect really.All the time it is not changed in compared to color in c, illustrates that the copper oxide nano material of imidodicarbonic diamide functionalization there is no oxidasic effect, and a cuvette quickly becomes blue, illustrates that PDI-CuO nano material can be used as the analogue enztme of peroxidase.
Being monitored reaction system with ultraviolet-visible spectrophotometer, result is as shown in Figure 4 simultaneously.
Interpretation of result: the absorbance of a substantially ratio b at 652nm, d, e system is high, it was demonstrated that the addition of PDI-CuO nano composite material promotes H2O2Reaction with TMB.And c system does not has absworption peak at 652, illustrate that PDI-CuO nano composite material does not has oxidasic effect.Result above also illustrate that, PDI-CuO nano composite material can be used as the analogue enztme of peroxidase.
Claims (8)
1. the preparation method of the cupric oxide nano composite of an imidodicarbonic diamide functionalization, it is characterised in that comprise the following steps:
(1) choosing imidodicarbonic diamide, DMF, water-soluble mantoquita, neopelex and NaOH are raw material；
(2) copper chloride and neopelex are dissolved in deionized water, and under agitation drip sodium hydroxide solution, obtain light blue solution；
(3), after aged at room temperature, suspension is obtained；
(4) suspension is transferred in reactor 100 DEG C be dried, by centrifugation, washs, be dried and calcining, prepare Copper oxide nano-belt；
(5) prepared cupric oxide is joined dissolve imidodicarbonic diamide DMF solution in, ultrasonic 0.5 h, by centrifugation, wash, be dried, prepare imidodicarbonic diamide functionalization cupric oxide nano composite.
The preparation method of the cupric oxide nano composite of a kind of imidodicarbonic diamide functionalization the most according to claim 1, it is characterised in that in step (1): described water-soluble mantoquita is water miscible copper chloride, copper nitrate, copper acetate.
The preparation method of the cupric oxide nano composite of a kind of imidodicarbonic diamide functionalization the most according to claim 1, it is characterised in that in step (1): described water-soluble mantoquita is 1:40～1:60 with the mol ratio of NaOH.
The preparation method of the cupric oxide nano composite of a kind of imidodicarbonic diamide functionalization the most according to claim 1, it is characterised in that in step (2): described concentration of sodium hydroxide solution is 4～6 mol/L.
The preparation method of the cupric oxide nano composite of a kind of imidodicarbonic diamide functionalization the most according to claim 1, it is characterised in that in step (3): described ageing time is 4～5 h.
The preparation method of the cupric oxide nano composite of a kind of imidodicarbonic diamide functionalization the most according to claim 1, it is characterised in that in step (4): described baking temperature is 90～110 DEG C.
The preparation method of the cupric oxide nano composite of a kind of imidodicarbonic diamide functionalization the most according to claim 1, it is characterised in that in step (4): described calcining heat is 350 DEG C.
The preparation method of the cupric oxide nano composite of a kind of imidodicarbonic diamide functionalization the most according to claim 1, it is characterised in that in step (5): the concentration of described imidodicarbonic diamide is 1
G/L～3 g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116873973A (en) * | 2023-07-12 | 2023-10-13 | 山东乾能科技创新有限公司 | La 0.5 Li 0.5 TiO 3 CuO nano material, MEMS propyl acetate sensor and preparation method |
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| CN103159771A (en) * | 2013-03-29 | 2013-06-19 | 山东科技大学 | Technique for synthesizing porphyrin-functionalized cobalt oxide nanoparticles by one-step method |
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Patent Citations (4)
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| CN102765746A (en) * | 2012-07-30 | 2012-11-07 | 济南大学 | Method for preparing flower-like nano cadmium sulfide by using perylene bisimide derivatives as template |
| CN103030169A (en) * | 2012-12-26 | 2013-04-10 | 中北大学 | Shape-controlled preparation method of nanometer copper oxide |
| CN103159771A (en) * | 2013-03-29 | 2013-06-19 | 山东科技大学 | Technique for synthesizing porphyrin-functionalized cobalt oxide nanoparticles by one-step method |
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Non-Patent Citations (2)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116873973A (en) * | 2023-07-12 | 2023-10-13 | 山东乾能科技创新有限公司 | La 0.5 Li 0.5 TiO 3 CuO nano material, MEMS propyl acetate sensor and preparation method |
| CN116873973B (en) * | 2023-07-12 | 2024-04-05 | 山东乾能科技创新有限公司 | La 0.5 Li 0.5 TiO 3 CuO nano material, MEMS propyl acetate sensor and preparation method |
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