CN111302333B - Room-temperature compounding method of graphene oxide and metal nanoparticles - Google Patents
Room-temperature compounding method of graphene oxide and metal nanoparticles Download PDFInfo
- Publication number
- CN111302333B CN111302333B CN202010101065.0A CN202010101065A CN111302333B CN 111302333 B CN111302333 B CN 111302333B CN 202010101065 A CN202010101065 A CN 202010101065A CN 111302333 B CN111302333 B CN 111302333B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- room temperature
- metal
- metal nanoparticles
- stirring
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for compounding graphene oxide and metal nanoparticles at room temperature, which comprises the following steps: putting graphene oxide into distilled water at room temperature, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid; taking 0.2-2.5 mmol/L metal salt solution, carrying out magnetic stirring at room temperature, heating to reflux after complete dissolution, adding 0.1-38.8 mmol/L reducing agent, and stirring at 25-100 ℃ for 15-60 min to obtain a metal nanoparticle solution; cooling to room temperature under the stirring condition, and adding 0.4-10 mmol/L stabilizer for ultrasonic self-assembly to obtain metal nanoparticles; and stirring the obtained graphene oxide dispersion liquid and the metal nanoparticles for reaction at room temperature, centrifuging and washing to obtain the graphene oxide and metal nanoparticle composite. The method has the advantages that the graphene material compounded by different metal nano particles can be obtained at room temperature through different metal salts, and can be widely applied to the fields of sensing detection, environmental protection, biological medical treatment and the like.
Description
Technical Field
The invention belongs to the technical field of new materials, nano materials and functionalized materials, and particularly relates to a method for directly preparing a graphene oxide metal nanoparticle compound at room temperature by a one-step blending method.
Background
The graphene oxide is an important graphene functionalized product of graphene, and the graphene oxide has good hydrophilic characteristics due to abundant oxygen-containing functional groups on the surface while retaining a plurality of characteristics of the graphene, can be stably dispersed in an aqueous solution, and can be intercalated and peeled by polymers such as small molecules and epoxy resin. And the surface of the graphene oxide contains reactive functional groups such as hydroxyl, carboxyl and the like, the surfaces of the graphene oxide are negatively charged by the groups, and the stability and the hydrophilic capacity of the graphene oxide in an aqueous phase system can be further improved by electrostatic repulsion between charges. Due to the excellent performance of the graphene oxide compound, the graphene oxide compound plays a very important role in improving the comprehensive properties of materials such as heat, electricity, mechanics and the like. The graphene oxide compound is developed very rapidly, and the application field of the graphene oxide can be further expanded.
The graphene oxide can be functionalized by utilizing a large amount of oxygen-containing groups such as carboxyl, hydroxyl and epoxy groups contained at the top and the bottom of the graphene oxide, the metal nanoparticles are compounded with the graphene oxide, and the metal nanoparticles are self-assembled on the surface of the graphene oxide through non-covalent bonds. The graphene oxide and metal nanoparticle composite has a small size effect, a surface effect, a quantum size effect, good biocompatibility, excellent catalytic performance and strong stability, so that the graphene oxide and metal nanoparticle composite can be widely applied to the fields of information electronics, biomedical treatment, sensing detection, energy conservation, environmental protection, energy industry and the like.
The main method for preparing the graphene oxide metal nanoparticle composite reported at present is generally an electrochemical reduction method, and the graphene oxide and metal nanoparticle composite is obtained by performing direct electrochemical reduction on the surface of a glassy carbon electrode and assembling metal nanoparticles. Such methods generally require high reaction conditions and low product yields, which are not conducive to large-scale production.
Disclosure of Invention
Aiming at the problems, the invention researches and designs a graphene oxide and metal nano particle room temperature composite method to solve the defects of high requirement on reaction conditions and limited production scale of the traditional composite method.
The technical means adopted by the invention are as follows:
a graphene oxide and metal nanoparticle room temperature compounding method comprises the following steps:
s1, placing graphene oxide into distilled water at room temperature, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
s2, taking 0.2-2.5 mmol/L metal salt solution, carrying out magnetic stirring at room temperature, heating to reflux after complete dissolution, simultaneously adding 0.1-38.8 mmol/L reducing agent, and stirring for 15-60 min at 25-100 ℃ to obtain a metal nanoparticle solution;
s3, adding 0.4-10 mmol/L stabilizer into the obtained metal nanoparticle solution at room temperature, and carrying out ultrasonic self-assembly to obtain metal nanoparticles for later use;
s4, stirring the obtained graphene oxide dispersion liquid and the metal nanoparticle solution at room temperature for reaction, and then centrifuging and washing to obtain a graphene oxide and metal nanoparticle compound;
wherein the stabilizer described in step S3 is: thioglycolic acid or mercaptopropionic acid.
Preferably, in step S2, the metal salt solution is one or a mixture of a gold salt solution and a silver salt solution.
Preferably, in step S2, the reducing agent is one or a mixture of sodium citrate and sodium borohydride.
Preferably, in step S2, the magnetic stirring speed is 300 to 750 r/min.
Preferably, in step S3, the stabilizer is one or more of mercaptoethylamine, mercaptoethanol, mercaptopropanol, mercaptoundecanamine, mercaptoundecanol, and mercaptoundecanoic acid.
Preferably, in step S4, the obtained graphene oxide and metal nanoparticle composite includes 10 to 99% of graphene oxide and 1 to 90% of metal nanoparticles by weight ratio, respectively.
Compared with the prior art, the room-temperature compounding method of the graphene oxide and the metal nanoparticles has the following beneficial effects:
1. the preparation condition is mild, the composite reaction can be carried out at room temperature, the operation is simple and easy, energy is saved, the environment is protected, and the method can be used for large-scale production;
2. the graphene oxide is combined with the metal nano particles in a non-covalent bond manner, and the sheet-like structure of the graphene oxide is well kept;
3. the composite ratio of the graphene oxide and the metal nanoparticles is controlled, so that the dispersion state of the metal nanoparticles can be effectively adjusted, and the metal nanoparticles are in a high dispersion state and are uniformly distributed in particle size;
4. the graphene oxide and metal nanoparticle composite can maintain the respective characteristics of the graphene oxide and the metal nanoparticles, and can expand the application range through a synergistic effect, and can be applied to the fields of sensing detection, environmental protection, biomedical treatment and the like.
Drawings
Fig. 1 is a TEM image of a graphene oxide and metal nanoparticle composite prepared in example 1;
fig. 2 is a TEM image of the graphene oxide and metal nanoparticle composite prepared in example 2;
fig. 3 is a TEM image of the graphene oxide and metal nanoparticle composite prepared in example 3.
Detailed Description
A graphene oxide and metal nanoparticle room temperature compounding method comprises the following steps:
preparing a graphene oxide dispersion liquid: and dispersing graphene oxide in distilled water at room temperature, and performing ultrasonic dispersion for 1h to obtain a graphene oxide dispersion liquid.
Preparing metal nanoparticles: taking 0.2-2.5 mmol/L metal salt solution, carrying out magnetic stirring at room temperature, heating to reflux after complete dissolution, simultaneously adding 0.1-38.8 mmol/L reducing agent, stirring the solution at 25-100 ℃ for 15-60 min to obtain metal nanoparticle solution, cooling the metal nanoparticle solution to room temperature under the stirring condition, adding 0.4-10 mmol/L stabilizing agent, and carrying out ultrasonic self-assembly to obtain metal nanoparticles for later use.
Preparing a graphene oxide and metal nanoparticle compound: and stirring the obtained graphene oxide dispersion liquid and the metal nanoparticle solution at room temperature for reaction, centrifuging and washing to obtain the graphene oxide dispersion liquid and the metal nanoparticle compound.
Further, the metal salt solution is one or a mixture of a gold salt solution and a silver salt solution; the reducing agent is one or a mixture of sodium citrate and sodium borohydride; the magnetic stirring speed is 300-750 r/min; the stabilizer is one or more than two of mercaptoethylamine, mercaptoethanol, mercaptoacetic acid, mercaptopropanol, mercaptopropionic acid, mercaptoundecylamine, mercaptoundecanol and mercaptoundecanoic acid; the obtained graphene oxide and metal nanoparticle composite comprises 10-99% of graphene oxide and 1-90% of metal nanoparticles in percentage by weight.
Example 1:
preparing a graphene oxide dispersion liquid: 0.5g of graphene oxide is dispersed in 500ml of distilled water solution, and ultrasonic treatment is carried out for 1 hour at room temperature to obtain graphene oxide solution for later use.
Preparing gold nanoparticles: heating and refluxing 100ml of chloroauric acid aqueous solution with the concentration of 0.24mmol/L to boiling under magnetic stirring, quickly adding newly-configured 0.85ml of trisodium citrate aqueous solution with the concentration of 28.7mmol/L, changing the solution from transparent faint yellow to black within 3min, finally changing the solution to purple red, continuously stirring and refluxing for 40min, cooling the sol to room temperature under the stirring condition, adding 1ml of thioglycolic acid with the concentration of 1mmol/L, and carrying out ultrasonic self-assembly to obtain the nanogold sol for later use.
Preparing a graphene oxide and gold nanoparticle composite: and (3) dispersing 10ml of the prepared nano gold sol into 10ml of graphene oxide solution with the concentration of 1mg/ml, stirring for 20min at room temperature, and centrifuging and washing to obtain the graphene oxide gold nanoparticle compound.
The compound obtained above was observed by a transmission electron microscope, and the result is shown in FIG. 1. The figure clearly shows that the nanogold/graphene oxide compound keeps the very thin silk-like skirt-crinkle layer shape of graphene oxide, nanogold particles are highly dispersed on the surface of the graphene oxide through non-covalent bonds, and the average particle size of the nanogold particles is 10 nm.
Example 2:
preparing a graphene oxide dispersion liquid: dispersing 0.5g of graphene oxide in 100ml of distilled water solution, and carrying out ultrasonic treatment for 1 hour at room temperature to obtain a graphene oxide solution for later use.
Preparing silver nano particles: heating 125ml of silver nitrate with the concentration of 2.4mmol/L to 100 ℃ under the stirring condition, quickly adding 5ml of newly-prepared trisodium citrate aqueous solution with the concentration of 31.6mmol/L, carrying out reflux reaction for 60min, stopping heating, continuing stirring, naturally cooling the nano-silver sol to room temperature under the stirring condition, adding 1ml of mercaptopropionic acid with the concentration of 1mmol/L, and carrying out ultrasonic self-assembly to obtain the nano-silver sol for later use.
Preparing a graphene oxide and silver nanoparticle compound: and (3) dispersing 10ml of the prepared nano silver sol into 10ml of graphene oxide solution with the concentration of 1mg/ml, stirring for 20min at room temperature, and centrifuging and washing to obtain the graphene oxide and silver nanoparticle compound.
The compound obtained above was observed by a transmission electron microscope, and the result is shown in FIG. 2. The figure clearly shows that the appearance of the thin silk-like skirt wrinkle layer of the graphene oxide is maintained, the nano silver particles are highly dispersed on the surface of the graphene oxide, and the average particle size of the nano silver particles is 30 nm.
Example 3:
and (3) preparing a graphene oxide dispersion liquid, namely dispersing 0.5g of graphene oxide in 100ml of distilled water solution, and performing ultrasonic treatment for 1 hour at room temperature to obtain a graphene oxide solution for later use.
Preparing gold nanoparticles: diluting 1ml of chloroauric acid aqueous solution with the concentration of 0.57mmol/L in 100ml of water under magnetic stirring, rapidly adding newly configured 1ml of sodium borohydride aqueous solution with the concentration of 0.12mmol/L, and strongly stirring at room temperature for 15min to obtain wine red nanogold sol for later use.
Preparing a graphene oxide gold nanoparticle compound: and (3) dispersing 15ml of the prepared gold nanoparticle solution in 10ml of graphene oxide solution with the concentration of 1mg/ml, stirring for 20min at room temperature, and centrifuging and washing to obtain the graphene oxide gold nanoparticle compound.
The compound obtained above was observed by a transmission electron microscope, and the result is shown in FIG. 3. The figure clearly shows that the compound obtained by compounding the gold nanoparticles prepared by the sodium borohydride reduction method with the graphene oxide also keeps the appearance of the thin silk-like skirt-crinkle layer of the graphene oxide, the gold nanoparticles are dispersed on the surface of the graphene oxide through non-covalent bonds, and the average particle size of the gold nanoparticles is 5 nm.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (5)
1. A graphene oxide and metal nano particle room temperature compounding method is characterized in that: the method comprises the following steps:
s1, putting the graphene oxide into distilled water at room temperature, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid;
s2, taking 0.2-2.5 mmol/L metal salt solution, carrying out magnetic stirring at room temperature, heating to reflux after complete dissolution, simultaneously adding 0.1-38.8 mmol/L reducing agent, and stirring for 15-60 min at 25-100 ℃ to obtain a metal nanoparticle solution;
s3, adding 0.4-10 mmol/L stabilizer into the obtained metal nanoparticle solution at room temperature, and carrying out ultrasonic self-assembly to obtain metal nanoparticles for later use;
s4, stirring the obtained graphene oxide dispersion liquid and the metal nanoparticle solution at room temperature for reaction, and then centrifuging and washing to obtain a graphene oxide and metal nanoparticle compound;
wherein the stabilizer described in step S3 is: thioglycolic acid or mercaptopropionic acid.
2. The method for compounding graphene oxide and metal nanoparticles at room temperature according to claim 1, wherein the method comprises the following steps: in step S2, the metal salt solution is one or a mixture of a gold salt solution and a silver salt solution.
3. The method for compounding graphene oxide and metal nanoparticles at room temperature according to claim 1, wherein the method comprises the following steps: in step S2, the reducing agent is one or a mixture of sodium citrate and sodium borohydride.
4. The method for compounding graphene oxide and metal nanoparticles at room temperature according to claim 1, wherein the method comprises the following steps: in step S2, the magnetic stirring speed is 300-750 r/min.
5. The method for compounding graphene oxide and metal nanoparticles at room temperature according to claim 1, wherein the method comprises the following steps: in step S4, the obtained graphene oxide and metal nanoparticle composite includes 10-99% graphene oxide and 1-90% metal nanoparticles by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010101065.0A CN111302333B (en) | 2020-02-19 | 2020-02-19 | Room-temperature compounding method of graphene oxide and metal nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010101065.0A CN111302333B (en) | 2020-02-19 | 2020-02-19 | Room-temperature compounding method of graphene oxide and metal nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111302333A CN111302333A (en) | 2020-06-19 |
| CN111302333B true CN111302333B (en) | 2022-09-16 |
Family
ID=71152852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010101065.0A Active CN111302333B (en) | 2020-02-19 | 2020-02-19 | Room-temperature compounding method of graphene oxide and metal nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111302333B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112376027A (en) * | 2020-11-13 | 2021-02-19 | 无锡华鑫检测技术有限公司 | Preparation method of graphene oxide metal nanosheet composite material |
| CN113930051B (en) * | 2021-11-03 | 2023-07-14 | 一汽解放汽车有限公司 | Carbon-based composite material and preparation method and application thereof |
| CN114203338B (en) * | 2021-11-16 | 2023-09-29 | 香港理工大学深圳研究院 | Conductive paste and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102085575A (en) * | 2009-12-03 | 2011-06-08 | 中国科学院化学研究所 | Method for rapidly and continuously preparing size and feature controllable metal nano particles |
| CN104254418A (en) * | 2011-11-03 | 2014-12-31 | 克拉里安特国际有限公司 | Method for producing a metal nanoparticle dispersion, metal nanoparticle dispersion, and use of said metal nanoparticle dispersion |
| CN106735286A (en) * | 2016-11-25 | 2017-05-31 | 湖北大学 | Graphene oxide/Jenner's nano composite material and its preparation method and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL227876B1 (en) * | 2014-02-13 | 2018-01-31 | Instytut Tech Materialow Elektronicznych | Suspension of graphene oxide nanoparticle flakes in water, its application and method for obtaining it |
| KR101630533B1 (en) * | 2014-11-03 | 2016-06-15 | 충남대학교산학협력단 | Manufacturing method of hyghly dispersible reduced graphene oxide based metal nanoparticle dispersion and metal nanoparticle film using thereof |
| CN110343522B (en) * | 2019-07-09 | 2022-01-14 | 江苏师范大学 | Preparation of gold @ graphene oxide composite nanomaterial and application of gold @ graphene oxide composite nanomaterial in adenosine triphosphate detection |
-
2020
- 2020-02-19 CN CN202010101065.0A patent/CN111302333B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102085575A (en) * | 2009-12-03 | 2011-06-08 | 中国科学院化学研究所 | Method for rapidly and continuously preparing size and feature controllable metal nano particles |
| CN104254418A (en) * | 2011-11-03 | 2014-12-31 | 克拉里安特国际有限公司 | Method for producing a metal nanoparticle dispersion, metal nanoparticle dispersion, and use of said metal nanoparticle dispersion |
| CN106735286A (en) * | 2016-11-25 | 2017-05-31 | 湖北大学 | Graphene oxide/Jenner's nano composite material and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111302333A (en) | 2020-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111302333B (en) | Room-temperature compounding method of graphene oxide and metal nanoparticles | |
| Li et al. | Fabrication of biosensor based on core–shell and large void structured magnetic mesoporous microspheres immobilized with laccase for dopamine detection | |
| CN103361885A (en) | Preparation method of antibacterial silk fibroin fibrous membrane | |
| CN107068319B (en) | A kind of preparation method of hydrophobic magnetic composite material | |
| CN103769583B (en) | The preparation method of the gold nano grain of modified by graphene quantum dot | |
| CN109604629B (en) | Composite material and preparation method and application thereof | |
| CN106969860A (en) | Intelligent Magnetic driving selfreparing flexible pressure-sensitive sensor and preparation method thereof | |
| CN110655755A (en) | Preparation method of silver nanoparticle loaded graphene-based epoxy resin composite material | |
| Manavalan et al. | Microwave-assisted synthesis of gadolinium (III) oxide decorated reduced graphene oxide nanocomposite for detection of hydrogen peroxide in biological and clinical samples | |
| Yang et al. | Synthesis of Ag/γ-AlOOH nanocomposites and their application for electrochemical sensing | |
| Ansari et al. | Deoxygenation of graphene oxide using biocompatible reducing agent Ficus carica (dried ripe fig) | |
| CN101538736A (en) | Dendritic golden nanophase material and preparation method thereof | |
| CN101920940A (en) | Method for preparing tellurium nanocrystals | |
| WO2024087551A1 (en) | Method for preparing silver nanowires using soft template method | |
| Sai-Dan et al. | Application of inorganic layered materials in electrochemical sensors | |
| CN113787194A (en) | Method for forming ultra-small-size and high-density nano silver particles by utilizing tannic acid coating to assist surface in-situ reduction of phenolic resin microspheres | |
| CN102614869A (en) | Preparation method of amino functionalization porous palladium nanospheres | |
| CN113680291B (en) | Preparation method of paramagnetic metal oxide/spinel/carbon composite microsphere | |
| CN106916757B (en) | Single cell bio-based high-hydrophobicity micron powder material and preparation method thereof | |
| CN109364836A (en) | A kind of preparation method of the temperature sensitivity nano-reactor based on gold nanoparticle | |
| CN105923624A (en) | Preparation method for modified graphene | |
| CN109856203A (en) | Mosaic alloy/titanium dioxide cerium tablet/carbon fiber composite nano materials preparation method and applications research | |
| Razak et al. | Metal Oxide nanostructure-modified Electrode for glucose biosensor | |
| CN111089883A (en) | Preparation method of nano-silver/graphene electrochemical sensor | |
| CN110040729A (en) | A kind of method that physics removing prepares graphene metal nanoparticle complex |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220819 Address after: A37, Area A, Open Shared Space, Second Floor, Technology Innovation and Breeding Center, Ordos High-tech Industrial Development Zone, Kangbashi District, Ordos City, Inner Mongolia Autonomous Region, 017010 Applicant after: Inner Mongolia new carbon material technology Co.,Ltd. Address before: 102200 No.37, Zhongxin South Street, Yangfang Town, Changping District, Beijing Applicant before: Dalian meisene New Material Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |