CN109745983A - A kind of preparation method and applications for the copper nano particles that graphene quantum dot is stable - Google Patents
A kind of preparation method and applications for the copper nano particles that graphene quantum dot is stable Download PDFInfo
- Publication number
- CN109745983A CN109745983A CN201910081985.8A CN201910081985A CN109745983A CN 109745983 A CN109745983 A CN 109745983A CN 201910081985 A CN201910081985 A CN 201910081985A CN 109745983 A CN109745983 A CN 109745983A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- nano particles
- copper nano
- graphene quantum
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention provides a kind of new methods for preparing copper nano particles, belong to the technical field of nanometer synthetic method, prepare copper nano particles using graphene quantum dot, it is easy to operate, reaction condition is mild, and copper nano particles obtained are very stable, and monodispersity can be good.The present invention first uses the aqueous solution of graphene quantum dot, and sodium borohydride aqueous solution is added and stable copper nano particles are made in anhydrous slufuric acid copper liquor.Copper nano particles obtained are dispersed in the solution of clear, and copper nano-scale is in several nanometers between tens nanometers, and the stability of solution is very good.Using the copper nano particles that graphene quantum dot is stable, as the catalyst to the Isosorbide-5-Nitrae-two of preparation regioselectivity replaces -1,2,3- triazoles.Method is simple, and green safe, not the generation of harmful substance, meets protection environment, the green principle at production.
Description
Technical field
The invention belongs to the technical fields of nano material synthetic method, stable more particularly, to a kind of graphene quantum dot
The preparation method of copper nano particles, and its application is to prepare a kind of triazole.
Background technique
Nano particle is because of its unique performance, such as quantum size effect, skin effect, interfacial effect, bulk effect, small ruler
Very little effect, macro quanta tunnel effect etc. cause the extensive concern of material and catalytic field, and nano particle technology of preparing is then
It is the important foundation of nano ZnO research and application.
Graphene quantum dot a member new as graphene family, it is smaller compared to traditional grapheme material,
Specific surface area is bigger, and in addition to the excellent properties with graphene, a system is also shown because of quantum limitation effect and boundary effect
The extensive concern of each field scientist such as new characteristic is arranged, therefore has attracted chemistry, physics, material and biology.
Traditional method prepares stable copper nano particles using other materials, the copper nano particles stability prepared
Difference, monodispersity is bad, and method is complex.Stable copper nano particles are prepared using graphene quantum dot, it is obtained
Copper nano particles stablize height, and monodispersity can well and method is simple.
Graphene quantum dot solution can be simply as reducing agent and the mixing of protective agent and anhydrous cupric sulfate, graphene quantum dot
The oxygen-containing functional group on surface can be by Cu2+It is reduced to Cu+, copper nano particles are grown in its surface in situ, prepare stability height,
The stable copper nano particles of the good graphene of monodispersity energy can pass through hydrogen since hydroxyl is contained on graphene quantum dot surface
Key effect is connected to copper nano-particle surface, inhibits itself reuniting for copper nano particles well, it is presented in water good
Good dispersibility.
The triazole of synthesis is a kind of particularly useful active medicine, has many interesting antibacterial activities, there is antiallergy
Activity, HIV-resistant activity, anti-tumor activity can be used as pesticide, medicine intermediate, be widely used in triadimefon, paclobutrazol, alkene
Imitate the synthesis of the pesticides such as azoles, olefin conversion.
The method for preparing stable metal nanoparticle using graphene quantum dot from the point of view of document report is very rare,
This triazole is prepared using the stable copper nano particles of graphene quantum dot, and there is not been reported.
Summary of the invention
The present invention is to have used a kind of new method for prepare stable copper nano particles, and with the copper nanometer synthesized
Grain is used to prepare triazole as catalyst.
Specific technical solution is as follows:
The preparation method of the stable copper nano particles of graphene quantum dot:
(1) synthesizing graphite alkene quantum dot: taking soluble starch, in container, water is added, in oil bath pan at 30-100 DEG C
Reaction kettle is poured into after stirring and dissolving, is put into 100-200 DEG C of reaction 2-10h of baking oven, and centrifugation can be prepared by graphene quantum dot solution；
(2) graphene quantum dot solution is taken, is stirred evenly after sodium borohydride aqueous solution is added, adds anhydrous slufuric acid copper water
Solution stirs evenly, and the stable copper nano particles of graphene quantum dot can be obtained after being stirred at room temperature uniformly.
The amount of the substance of the sodium borohydride is 15-20 times of the amount of added anhydrous slufuric acid copper material；Graphene quantum
The amount of the substance of anhydrous cupric sulfate added by point aqueous solution 1ml is 1 × 10-4mmol-5×10-3mmol。
The sodium borohydride aqueous solution using be added dropwise by the way of be added, rate of addition be every milliliter 1-10 minute, dropwise addition
Continue stirring 20-40 minutes after the completion.
The anhydrous slufuric acid copper solution using be added dropwise by the way of be added, rate of addition be every milliliter 1-10 minute, dropwise addition
Continue stirring 1-6 hours after the completion.
Another technical solution of the invention is being made the copper nano particles of graphene quantum dot obtained as catalyst
Application on standby triazole.Specific step is as follows:
It takes end alkynes and end azido-methyl to be added in test tube, the stable copper nano particles of graphene quantum dot is added,
Under 28-30 DEG C of water bath condition, react 24-28 hour, stir evenly, can regioselectivity prepare Isosorbide-5-Nitrae-two substitution -1,2,3-
Triazole, reaction equation are as follows:
Step 4: replace -1,2,3- triazoles to purify the Isosorbide-5-Nitrae-two of regioselectivity obtained, yield 88-90%,
Nuclear magnetic spectrogram is done in sampling.Added graphene quantum dot stable copper nano particles, end alkynes, end azido-methyl substance
The ratio between amount is 5.0 × 10-5-1.0×10-3: 5:6-10.
The end azido-methyl includes benzyl azide, 1- (azido-methyl) -4- bromobenzene, 1- (azido-methyl) -4- iodine
Benzene, 1- (azido-methyl) -4- methoxybenzene, any one in 1- (azido-methyl) -4- cyano benzene, the end alkynes includes
Phenylacetylene, to methyl phenylacetylene, to Methoxy-phenylacetylene, p-nitrophenylacetylene, to any one in bromobenzene acetylene.
The copper nano particles for the graphene quantum dot that the ratio between institute of the invention obtains take in the 1,4- bis- for preparing regioselectivity
The generation reaction process of -1,2,3- triazoles is as shown below, is catalyzed generally by Cu (I), and alkynyl occurs ring with azido and adds
At reaction, the Isosorbide-5-Nitrae-two of formation zone selectivity replaces -1,2,3- triazoles.
The graphene quantum dot solution being prepared in the present invention can be simply as reducing agent and protective agent and anhydrous slufuric acid
Copper mixing, the oxygen-containing functional group on graphene quantum dot surface can be by Cu2+It is reduced to Cu+, surface contains hydroxyl, can pass through hydrogen
Key effect is connected to copper nano-particle surface, inhibits itself reuniting for copper nano particles well, it is presented in water good
Good dispersibility.
Detailed description of the invention
Fig. 1 is the reaction mechanism of the bis- substitution -1,2,3- triazole of 1,4- of regioselectivity.
Fig. 2 is the scanning electron microscope (SEM) photograph of the stable copper nano particles of the graphene quantum dot of the preparation of embodiment 1.
Fig. 3 is the particle diameter distribution frequency of copper nanometer in the stable copper nano particles of the graphene quantum dot of the preparation of embodiment 1
Statistics.
Fig. 4 is the scanning electron microscope (SEM) photograph of the stable copper nano particles of the graphene quantum dot of the preparation of embodiment 2.
Fig. 5 is the 1- benzyl -4- phenyl -1H- of the stable copper nano particles preparation of graphene quantum dot produced by the present invention
The 1H-NMR spectrogram of 1,2,3-triazoles.
Specific embodiment
Embodiment 1
Step 1: taking 1ml graphene quantum dot solution, be added in reagent bottle, stir 5 minutes.
Step 2: 2ml deionized water is added, stirs 5 minutes.
Step 3: 1ml sodium borohydride solution is added, the amount of added sodium borohydride substance is anhydrous cupric sulfate added by step 3
20 times of the amount of substance.Rate of addition be every milliliter 1-5 minutes.
Step 4: 1ml anhydrous slufuric acid copper liquor is added, the amount of added anhydrous slufuric acid copper material is 2.5 × 10-3Mmol, drop
Acceleration be every milliliter 1-5 minutes.Then it stirs 2-3 hours.The stable copper nano particles of graphene are made.Characteristic electricity is done in sampling
Scarnning mirror figure.
Fig. 2 is the characteristic electron-microscope scanning figure of the stable copper nano particles of the graphene quantum dot of embodiment 1.Black on figure
The substance of small ball shape is copper nano particles, this Detailed description of the invention graphene obtained stable copper nano particles particle size
Between 1-20nm.
Embodiment 2
Step 1: taking 1ml graphene quantum dot solution, be added in reagent bottle, stir 5 minutes.
Step 2: 2ml deionized water is added, stirs 5 minutes.
Step 3: 1ml sodium borohydride solution is added, the amount of added sodium borohydride substance is anhydrous cupric sulfate added by step 3
20 times of the amount of substance.Rate of addition be every milliliter 1-5 minutes.
Step 4: 1ml anhydrous slufuric acid copper liquor is added, the amount of added anhydrous slufuric acid copper material is 2.5 × 10-4Mmol, drop
Acceleration be every milliliter 1-5 minutes.Then it stirs 2-3 hours.The stable copper nano particles of graphene are made.Scanning electricity is done in sampling
Mirror.
Fig. 4 is the scanning electron microscope (SEM) photograph of the stable copper nano particles of the graphene quantum dot of embodiment 2.White roundlet on figure
The substance of ball shape is copper nano particles.This Detailed description of the invention graphene obtained stable copper nano particles particle size is in 1-
Between 100nm.
Embodiment 3
Step 1: phenylacetylene 0.5mmol and benzyl azide 0.8mmol being taken to be added in test tube；
Step 2: deionized water is added in the stable copper nano particles of the graphene quantum dot that addition embodiment 1 is prepared
2ml,
Step 3: test tube being immersed in 28-30 DEG C under water, is reacted 26 hours, is stirred evenly, 1- benzyl -4- can be prepared into
Phenyl -1H-1,2,3- triazoles, reaction equation are as follows:
The stable copper nano particles amount of substance of added graphene quantum dot is 1 × 10-3MM.
Step 4: by obtained 1- benzyl -4- phenyl -1H-1,2,3- triazoles are purified, yield 90.0%, and purity is
Nuclear magnetic spectrogram is done in 100.0% sampling.
Fig. 5 is 1- benzyl -4- phenyl -1H-1 made from the stable copper nano particles of graphene quantum dot of embodiment 3,2,
The 1H-NMR spectrogram of 3- triazole.This Detailed description of the invention substance obtained is actually 1- benzyl -4- phenyl -1H-1,2,3- triazoles.
Embodiment 4
Step 1: phenylacetylene 0.5mmol and benzyl azide 0.6mmol being taken to be added in test tube；
Step 2: deionized water is added in the stable copper nano particles of the graphene quantum dot that addition embodiment 1 is prepared
3ml,
Step 3: test tube being immersed in 28-30 DEG C under water, is reacted 28 hours, is stirred evenly, 1- benzyl -4- can be prepared into
Phenyl -1H-1,2,3- triazoles, reaction equation are as follows:
The stable copper nano particles amount of substance of added graphene quantum dot is 5 × 10-4MM.
Step 4: by obtained 1- benzyl -4- phenyl -1H-1,2,3- triazoles are purified, yield 88.5%, and purity is
100.0%.
Claims (8)
1. a kind of preparation method for the copper nano particles that graphene quantum dot is stable, which is characterized in that include the following steps:
(1) synthesizing graphite alkene quantum dot: taking soluble starch, in container, water is added, stirs at 30-100 DEG C in oil bath pan
Reaction kettle is poured into after dissolution, is put into 100-200 DEG C of reaction 2-10h of baking oven, and centrifugation can be prepared by graphene quantum dot solution；
(2) graphene quantum dot solution is taken, is stirred evenly after sodium borohydride aqueous solution is added, it is water-soluble to add anhydrous cupric sulfate
Liquid stirs evenly, and the stable copper nano particles of graphene quantum dot can be obtained after being stirred at room temperature uniformly.
2. the preparation method of the stable copper nano particles of graphene quantum dot according to claim 1, which is characterized in that boron
The amount of the substance of sodium hydride is 15-20 times of the amount of added anhydrous slufuric acid copper material；Nothing added by graphene quantum dot aqueous solution 1ml
The amount of the substance of brochanite is 1 × 10-4mmol-5×10-3mmol。
3. the preparation method of the stable copper nano particles of graphene quantum dot according to claim 1, which is characterized in that boron
Sodium hydride aqueous solution using be added dropwise by the way of be added, rate of addition be every milliliter 1-10 minute, continue after being added dropwise to complete stirring 20-
40 minutes.
4. the preparation method of the stable copper nano particles of graphene quantum dot according to claim 1, which is characterized in that nothing
Brochanite solution using be added dropwise by the way of be added, rate of addition be every milliliter 1-10 minute, continue after being added dropwise to complete stirring 1-6
Hour.
5. the copper nano particles of graphene quantum dot made from claim 1 are preparing the application on triazole as catalyst.
6. application described in claim 5, which is characterized in that preparing triazole, specific step is as follows:
It takes end alkynes and end azido-methyl to be added to the container, the stable copper nano particles of graphene quantum dot is added, in 28-30
It under DEG C water bath condition, reacts 24-28 hour, stirs evenly, -1,2,3- tri- nitrogen of substitution of Isosorbide-5-Nitrae-two of regioselectivity can be prepared
Azoles, reaction equation are as follows:
7. application according to claim 6, which is characterized in that the stable copper nano particles of added graphene quantum dot,
The ratio between amount of substance of end alkynes, end azido-methyl is 5.0 × 10-5-1.0×10-3: 5:6-10.
8. application according to claim 6, which is characterized in that the end azido-methyl includes benzyl azide, 1- (folded
N-methyl) -4- bromobenzene, 1- (azido-methyl) -4- iodobenzene, 1- (azido-methyl) -4- methoxybenzene, 1- (azido-methyl) -4- cyanogen
Any one in base benzene；The end alkynes include phenylacetylene, to methyl phenylacetylene, to Methoxy-phenylacetylene, to chlorobenzene second
Alkynes, to any one in bromobenzene acetylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910081985.8A CN109745983B (en) | 2019-01-28 | 2019-01-28 | Preparation method and application of copper nanoparticles with stable graphene quantum dots |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910081985.8A CN109745983B (en) | 2019-01-28 | 2019-01-28 | Preparation method and application of copper nanoparticles with stable graphene quantum dots |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109745983A true CN109745983A (en) | 2019-05-14 |
| CN109745983B CN109745983B (en) | 2021-10-19 |
Family
ID=66406385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910081985.8A Active CN109745983B (en) | 2019-01-28 | 2019-01-28 | Preparation method and application of copper nanoparticles with stable graphene quantum dots |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109745983B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812754A (en) * | 2021-02-07 | 2021-05-18 | 广西师范大学 | Phenylacetylene functionalized graphene/copper composite heat conduction material and preparation method thereof |
| CN113369486A (en) * | 2021-06-17 | 2021-09-10 | 中科检测技术服务(重庆)有限公司 | Preparation method of nano-copper particles for solar cell panel |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130050167A (en) * | 2011-11-07 | 2013-05-15 | 삼성전자주식회사 | A method for manufacturing graphene quantum dot and graphene quantum dot manufactured by the same |
| CN103769583A (en) * | 2014-03-03 | 2014-05-07 | 上海交通大学 | Preparation method of gold nanoparticle modified by graphene quantum dots |
| CN105061340A (en) * | 2015-08-31 | 2015-11-18 | 河南师范大学 | Method for preparing 1,2,3-triazoie compound through active-carbon-carried nano-copper catalyst in catalyzed synthesis mode |
| CN108097245A (en) * | 2017-11-13 | 2018-06-01 | 天津宝兴威科技股份有限公司 | A kind of preparation method of graphene quantum dot load Nano silver grain |
| CN108636407A (en) * | 2018-05-17 | 2018-10-12 | 江苏大学 | Preparation method based on graphene-supported copper nano-particle |
| CN108892130A (en) * | 2018-04-04 | 2018-11-27 | 三峡大学 | The green synthesis method of graphene quantum dot is prepared using starch |
| CN109020891A (en) * | 2018-09-05 | 2018-12-18 | 西北师范大学 | The synthesis of one type zeolitic imidazolate framework material Cu-ZIF and application as catalyst |
-
2019
- 2019-01-28 CN CN201910081985.8A patent/CN109745983B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130050167A (en) * | 2011-11-07 | 2013-05-15 | 삼성전자주식회사 | A method for manufacturing graphene quantum dot and graphene quantum dot manufactured by the same |
| CN103769583A (en) * | 2014-03-03 | 2014-05-07 | 上海交通大学 | Preparation method of gold nanoparticle modified by graphene quantum dots |
| CN105061340A (en) * | 2015-08-31 | 2015-11-18 | 河南师范大学 | Method for preparing 1,2,3-triazoie compound through active-carbon-carried nano-copper catalyst in catalyzed synthesis mode |
| CN108097245A (en) * | 2017-11-13 | 2018-06-01 | 天津宝兴威科技股份有限公司 | A kind of preparation method of graphene quantum dot load Nano silver grain |
| CN108892130A (en) * | 2018-04-04 | 2018-11-27 | 三峡大学 | The green synthesis method of graphene quantum dot is prepared using starch |
| CN108636407A (en) * | 2018-05-17 | 2018-10-12 | 江苏大学 | Preparation method based on graphene-supported copper nano-particle |
| CN109020891A (en) * | 2018-09-05 | 2018-12-18 | 西北师范大学 | The synthesis of one type zeolitic imidazolate framework material Cu-ZIF and application as catalyst |
Non-Patent Citations (1)
| Title |
|---|
| VSEVOLOD V ET AL: "A Stepwise Huisgen Cycloaddition Process: Copper(I)-Catalyzed Regioselective"Ligation"of Azides and Terminal Alkynes", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812754A (en) * | 2021-02-07 | 2021-05-18 | 广西师范大学 | Phenylacetylene functionalized graphene/copper composite heat conduction material and preparation method thereof |
| CN112812754B (en) * | 2021-02-07 | 2021-07-16 | 广西师范大学 | Phenylacetylene functionalized graphene/copper composite heat conduction material and preparation method thereof |
| CN113369486A (en) * | 2021-06-17 | 2021-09-10 | 中科检测技术服务(重庆)有限公司 | Preparation method of nano-copper particles for solar cell panel |
| CN113369486B (en) * | 2021-06-17 | 2023-06-16 | 中科检测技术服务(重庆)有限公司 | Preparation method of nano copper particles for solar cell panel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109745983B (en) | 2021-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1790612B1 (en) | Method for manufacturing a carbon nanotube | |
| CN103100725B (en) | Preparation method of silver/carbon quantum dot composite nanometer materials | |
| CN104028269B (en) | Graphene loaded metal nano composite material, and preparation method and application thereof | |
| CN108453265B (en) | Silicon dioxide nanotube confinement nickel nanoparticle and preparation method thereof | |
| JP5467252B2 (en) | Silver nanowire manufacturing method and silver nanowire | |
| CN102641736A (en) | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof | |
| WO2011131008A1 (en) | Method for preparing nano-nickel powder with microchannel reactor | |
| CN104689820B (en) | Cobalt-based bimetallic catalyst and its preparation method and application with column structure | |
| CN101618895A (en) | Multi-level structure alpha type nickel hydroxide prepared by microwave auxiliary and method thereof | |
| CN109745983A (en) | A kind of preparation method and applications for the copper nano particles that graphene quantum dot is stable | |
| CN102837004A (en) | Preparation method of polyhedral copper nanoparticle | |
| CN108817414B (en) | Preparation method of gold nanoflower in ionic liquid aqueous solution | |
| Ge et al. | Preparation and characterization of ultrafine Fe-O compound/ammonium perchlorate nanocomposites via in-suit growth method | |
| JP2021529716A (en) | A method for synthesizing high-purity carbon nanocoils based on a composite catalyst consisting of multiple small-sized catalysts. | |
| CN110842212A (en) | Superfine Pd tetrahedral nano material and preparation method and application thereof | |
| CN106947090A (en) | A kind of preparation method of MIL 100 (Fe) complex nanosphere | |
| CN114427104A (en) | Copper phthalocyanine polymer @ copper nanowire core-shell nano material as well as preparation method and application thereof | |
| CN104475107B (en) | The bimetallic sea urchin type catalyst being hydrogenated with for aromatic rings and its preparation method and application | |
| KR101341900B1 (en) | Manufacuring method of nano metal-graphene composite, and nano metal-graphene composite made by the same | |
| CN105290414A (en) | Method for synthesizing nano-copper particles | |
| CN109293940B (en) | One-dimensional HKUST-1 nanobelt and preparation method thereof | |
| CN113976879B (en) | Carbon layer coated ferrocobalt nano core-shell structure and preparation method thereof | |
| CN101260564A (en) | Method for preparing micron/nano tungsten oxide crystal whisker/wire/bar | |
| CN109865483A (en) | A kind of supersonically preparation method of gold/porous palladium Core-shell Structure Nanoparticles | |
| CN108393500A (en) | A kind of Mo-Ni alloy nano particles composite material and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |