CN104399998A - Preparation method of graphene/nano-silver composite material - Google Patents
Preparation method of graphene/nano-silver composite material Download PDFInfo
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- CN104399998A CN104399998A CN201410565427.6A CN201410565427A CN104399998A CN 104399998 A CN104399998 A CN 104399998A CN 201410565427 A CN201410565427 A CN 201410565427A CN 104399998 A CN104399998 A CN 104399998A
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Abstract
The invention relates to a preparation method of a graphene/nano-silver composite material. The method comprises the following steps: dissolving propylene glycol ethers of methylcellulose in de-ionized water, and performing ultrasonic treatment for 1-12 hours at a liquor ratio of 1:50; then adding 2-10g/L sodium periodate, performing a photophobic reaction at a temperature of 40-80 DEG C for 10-60 minutes, repeatedly cleaning with deionized water, centrifuging and drying for later use; mixing a 0.1-100g/L modified hydroxypropyl methyl cellulose water solution, a 0.1-100g/L silver-ammonia solution and a 0.01-0.5g/L graphene oxide solution at a volume ratio of (10:1:1)-(1:1:1), and performing ultrasonic treatment at a temperature of 40-100 DEG C for 1-12 hours; then transferring to a teflon-lined hydrothermal reaction kettle, performing heat preservation at 160-220 DEG C for 1-48 hours, naturally cooling, repeatedly cleaning with ethanol and deionized water, centrifuging, and drying to obtain the graphene/nano-silver composite material. Graphene oxide and a silver-ammonia solution are utilized as raw materials, and the hydroxypropyl methyl cellulose water solution modified by sodium periodate is taken as a reducing agent, so that the graphene/nano-silver composite material is prepared by a one-step method under the condition of not adding any stabilizer or dispersing agent. The preparation method has the advantages of simple process, wide raw material sources, wild reaction, environmental friendliness and the like.
Description
Technical field
The invention belongs to technical field of nano material, particularly a kind of preparation method of graphene/nano silver composite.
Background technology
2004, Univ Manchester UK physicist An Deliehaimu and Constantine Nuo Woxiaoluofu, utilize the method for tearing adhesive tape, from graphite, successfully isolate the Graphene of individual layer atomic arrangement, therefore two people also obtain the Nobel Prize in physics (Science of 2010,2004,306 (5696): 666-669).Graphene by carbon atom with sp
2hybridized orbit composition hexangle type honeycomb lattice, its construction unit is carbon hexatomic ring, and it is a kind of two-dimensional material only having monolayer carbon atomic thickness.Graphene is the basic system unit forming carbon-based material.It can be wrapped to form zero dimension Fullerenes, is rolled into one dimension carbon nanotube, is piled into three-dimensional graphite layer by layer.From that day that Graphene finds, Graphene has just become focus and the focus of research, is widely used in fields such as ultracapacitor, transparency electrode, desalinization, light emitting diode, sensor, Chu Qing, solar cell, catalyst carrier, composite, biologic bracket material, bio-imaging, drug delivery, weaving, printing and dyeing.
Nano Silver has excellent conductivity of heat, electric conductivity, surface-active and catalytic performance, has huge using value in optics, catalysis, microelectronics, bio-sensing, the field such as antibacterial.
Graphene is the two-dimentional graphitic carbon material of monoatomic thickness, there is a series of excellent properties such as high-specific surface area, outstanding heat conductivility and mechanical property, outstanding electron transmission performance, it is the ideal carrier of Nano Silver, and the nano silver particles be present between graphene layer can play the contiguous graphene sheet layer of separation, prevent Graphene from the effect of reuniting occurring.Have many documents in recent years or patent reports the Synthesis and applications of nanometer silver-graphene composite material, but their poisonous hydrazine and sodium borohydrides of adopting as reducing agent more.Such as Jianfeng Shen etc. utilize the mixing reducing agent of sodium borohydride and ethylene glycol to prepare Graphene silver nano particle composite material (Nano Res., 2010,3 (5): 339-349).
In recent years, green, environmental protection, efficient and cheap method is adopted to prepare the focus that Nano Silver, Graphene and nanometer silver-graphene composite material become research gradually.He Guangyu etc. are that reducing agent passes through hydro-thermal reaction with polyethylene glycol, redox graphene is simultaneously at graphenic surface growth in situ Nano silver grain, prepare Nano Silver@graphene composite material, have studied the bacteriostasis property of composite simultaneously, result shows that Nano Silver@graphene composite material is a kind of Novel antibacterial material (fine chemistry industry of Be very effective, 2012,09:840-843).Chinese invention patent CN201210054952.2 adopts N, dinethylformamide (DMF) as reducing agent, the graphene powder of high purity 99% as carrier, under the reaction condition of gentleness, silver on graphene layer forming core, grow up, obtain Graphene/silver nano particle composite material.
Hydroxypropyl methylcellulose, has another name called Hydroxypropyl methylcellulose, HPMC, is to select the gossypin of high purity as raw material, obtains in the basic conditions through special etherificate.Hydroxypropyl methylcellulose water soluble and segment polarity solvent, can be used for the industry such as building, chemistry, cosmetics, food, medicine.
Selective oxidation refers to the oxidation suppressing other position hydroxyl while certain ad-hoc location hydroxyl of oxycellulose, and effectively can suppress cellulosic degraded in oxidation reaction process.After sodium metaperiodate selective oxidation cellulose, can by C
2, C
3hydroxyl oxygen on position changes into aldehyde radical, for cellulosic functional modification provides reactivity point, active aldehyde radical can be utilized to carry out functional modification to cellulose, can generate numerous functional fiber element derivative, greatly expand cellulosic range of application.Yet there are no with sodium metaperiodate selective oxidation hydroxypropyl methylcellulose as reducing agent one-step method prepares the report of graphene/nano silver composite.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of preparation method of graphene/nano silver composite is provided.
Present invention employs following technical scheme: be dissolved in by hydroxypropyl methylcellulose in deionized water, bath raio 1:50, ultrasonic 1-12h, add the sodium metaperiodate of 2-10g/L subsequently, at 40-80 DEG C, lucifuge reaction 10-60min, cleans repeatedly by deionized water, centrifugal, dry for standby; According to the volume ratio of 10:1:1-1:1:1, by the modification hydroxypropyl methylcellulose aqueous solution of 0.1-100g/L, mix with the silver ammino solution of 0.1-100g/L, the graphene oxide solution of 0.01-0.5g/L, ultrasonic 1-12h under the temperature conditions of 40 DEG C-100 DEG C, then move to 160-220 DEG C of insulation 1-48h in teflon-lined hydrothermal reaction kettle, naturally after cooling, repeatedly clean by ethanol and deionized water, centrifugal, obtain graphene/nano silver composite after dry process.
Preferably, silver ammino solution is the complex compound that nitrate or silver sulfate and ammoniacal liquor are formed.
Preferably, graphene oxide is obtained through ultrasonic delamination by graphite oxide, is single-layer graphene oxide, multilayer graphene oxide or the mixture of the two.
The present invention has following beneficial effect:
The present invention utilizes graphene oxide, silver-colored ammonia is raw material, the hydroxypropyl methylcellulose adopting sodium metaperiodate modified is as reducing agent, under the condition of not adding any stabilizing agent/dispersant, one-step method obtains graphene/nano silver composite, possess that technique is simple, raw material sources extensively, reaction temperature and, the advantage such as environmental protection.
Detailed description of the invention
Below in conjunction with detailed description of the invention, set forth the present invention further.
Embodiment 1:
Be dissolved in by 2g hydroxypropyl methylcellulose in 100ml deionized water, ultrasonic 1h, add the sodium metaperiodate of 2g/L subsequently, at 80 DEG C, lucifuge reaction 60min, cleans repeatedly by deionized water, centrifugal, dry for standby;
Hydroxypropyl methylcellulose modified for 1g is dissolved in 100ml deionized water, obtain the aqueous solution of the modification hydroxypropyl methylcellulose of concentration 10g/L, mix with the silver ammino solution of the 10g/L of 10ml, the graphene oxide solution of the 0.1g/L of 10ml mixes, ultrasonic 8h under the temperature conditions of 40 DEG C, then 160 DEG C of insulation 24h in teflon-lined hydrothermal reaction kettle are moved to, naturally after cooling, repeatedly clean by ethanol and deionized water, centrifugal, obtain graphene/nano silver composite after dry process.
Embodiment 2:
Be dissolved in by 2g hydroxypropyl methylcellulose in 100ml deionized water, ultrasonic 5h, add the sodium metaperiodate of 5g/L subsequently, at 60 DEG C, lucifuge reaction 30min, cleans repeatedly by deionized water, centrifugal, dry for standby;
Hydroxypropyl methylcellulose modified for 1g is dissolved in 50ml deionized water, obtain the aqueous solution of the modification hydroxypropyl methylcellulose of concentration 20g/L, mix with the silver ammino solution of the 20g/L of 10ml, the graphene oxide solution of the 0.5g/L of 10ml mixes, ultrasonic 5h under the temperature conditions of 60 DEG C, then 200 DEG C of insulation 15h in teflon-lined hydrothermal reaction kettle are moved to, naturally after cooling, repeatedly clean by ethanol and deionized water, centrifugal, obtain graphene/nano silver composite after dry process.
Embodiment 3:
Be dissolved in by 2g hydroxypropyl methylcellulose in 100ml deionized water, ultrasonic 10h, add the sodium metaperiodate of 10g/L subsequently, at 40 DEG C, lucifuge reaction 10min, cleans repeatedly by deionized water, centrifugal, dry for standby;
Hydroxypropyl methylcellulose modified for 1g is dissolved in 20ml deionized water, obtain the aqueous solution of the modification hydroxypropyl methylcellulose of concentration 50g/L, mix with the graphene oxide solution of the silver ammino solution of the 50g/L of 10ml, the 0.05g/L of 10ml, ultrasonic 1-12h under the temperature conditions of 40 DEG C-100 DEG C, then 160-220 DEG C of insulation 1-48h in teflon-lined hydrothermal reaction kettle is moved to, naturally after cooling, repeatedly clean by ethanol and deionized water, centrifugal, obtain graphene/nano silver composite after dry process.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of amplifying out or variation be still in the row of protection scope of the present invention.
Claims (6)
1. a preparation method for graphene/nano silver composite, is characterized in that:
(1) be dissolved in deionized water by hydroxypropyl methylcellulose, bath raio 1:50, ultrasonic 1-12h, add the sodium metaperiodate of 2-10g/L subsequently, at 40-80 DEG C, lucifuge reaction 10-60min, cleans repeatedly by deionized water, centrifugal, dry for standby;
(2) according to the volume ratio of 10:1:1-1:1:1, by the modification hydroxypropyl methylcellulose aqueous solution of 0.1-100g/L, mix with certain density silver ammino solution, certain density graphene oxide solution, ultrasonic 1-12h under the temperature conditions of 40 DEG C-100 DEG C, then move to 160-220 DEG C of insulation 1-48h in teflon-lined hydrothermal reaction kettle, naturally after cooling, repeatedly clean by ethanol and deionized water, centrifugal, obtain graphene/nano silver composite after dry process.
2. the preparation method of a kind of graphene/nano silver composite according to claim 1, is characterized in that, described volume ratio is 10:1:1-1:1:1.
3. the preparation method of a kind of graphene/nano silver composite according to claim 1, is characterized in that, described silver ammino solution is the complex compound that nitrate or silver sulfate and ammoniacal liquor are formed.
4. the preparation method of a kind of graphene/nano silver composite according to claim 1, is characterized in that, the concentration of described silver ammino solution is 0.1-100g/L.
5. the preparation method of a kind of graphene/nano silver composite according to claim 1, it is characterized in that, described graphene oxide is obtained through ultrasonic delamination by graphite oxide, is single-layer graphene oxide, multilayer graphene oxide or the mixture of the two.
6. the preparation method of a kind of graphene/nano silver composite according to claim 1, is characterized in that, the concentration of described graphene oxide is 0.01-0.5g/L.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104831389A (en) * | 2015-05-22 | 2015-08-12 | 济南圣泉集团股份有限公司 | Multifunctional viscose and preparation method thereof |
| CN105044186A (en) * | 2015-06-03 | 2015-11-11 | 西北师范大学 | Preparation method of porous graphene-peroxidase modified glassy carbon electrode |
| CN106063491A (en) * | 2016-05-16 | 2016-11-02 | 嵊州市润达助剂厂 | A kind of Graphene antibiosis agent and preparation method thereof |
| CN106270552A (en) * | 2016-08-16 | 2017-01-04 | 南昌大学 | A kind of preparation method of silver/graphite alkene nano composite material |
| CN107602943A (en) * | 2017-09-17 | 2018-01-19 | 赵兵 | The three-dimensional porous composite of cellulose base of supported nano zinc oxide |
| CN108219179A (en) * | 2017-12-14 | 2018-06-29 | 华南理工大学 | A kind of plant nanometer cellulose base flexible electromagnetic shielding film and its preparation method and application |
| CN108962619A (en) * | 2018-07-15 | 2018-12-07 | 重庆文理学院 | A kind of laminated film and preparation method thereof for flexible electrode |
| CN109354011A (en) * | 2018-11-17 | 2019-02-19 | 璧典附 | A kind of environment-friendly preparation method thereof of graphene |
| CN109368623A (en) * | 2018-09-20 | 2019-02-22 | 苏州博努奇纺织有限公司 | A kind of nano metal intercalated graphite alkene preparation method |
| CN110946148A (en) * | 2019-11-29 | 2020-04-03 | 陕西速源节能科技有限公司 | Preparation method of environment-friendly antibacterial agent |
| CN111099583A (en) * | 2018-10-26 | 2020-05-05 | 南京化学工业园环保产业协同创新有限公司 | Efficient composite synthesis method of graphene and nano-silver |
| CN116671515A (en) * | 2023-04-23 | 2023-09-01 | 合创(广州)科技研究有限公司 | Nano silver antibacterial liquid and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104831389A (en) * | 2015-05-22 | 2015-08-12 | 济南圣泉集团股份有限公司 | Multifunctional viscose and preparation method thereof |
| US10544520B2 (en) | 2015-05-22 | 2020-01-28 | Jinan Shengquan Group Share Holding Co., Ltd. | Multifunctional viscose fiber and preparation method therefor |
| CN105044186A (en) * | 2015-06-03 | 2015-11-11 | 西北师范大学 | Preparation method of porous graphene-peroxidase modified glassy carbon electrode |
| CN105044186B (en) * | 2015-06-03 | 2017-06-30 | 西北师范大学 | A kind of preparation method of poroid Graphene HRPO modified glassy carbon electrode |
| CN106063491A (en) * | 2016-05-16 | 2016-11-02 | 嵊州市润达助剂厂 | A kind of Graphene antibiosis agent and preparation method thereof |
| CN106270552B (en) * | 2016-08-16 | 2018-12-07 | 南昌大学 | A kind of preparation method of silver/graphite alkene nanocomposite |
| CN106270552A (en) * | 2016-08-16 | 2017-01-04 | 南昌大学 | A kind of preparation method of silver/graphite alkene nano composite material |
| CN107602943A (en) * | 2017-09-17 | 2018-01-19 | 赵兵 | The three-dimensional porous composite of cellulose base of supported nano zinc oxide |
| CN108219179A (en) * | 2017-12-14 | 2018-06-29 | 华南理工大学 | A kind of plant nanometer cellulose base flexible electromagnetic shielding film and its preparation method and application |
| CN108962619A (en) * | 2018-07-15 | 2018-12-07 | 重庆文理学院 | A kind of laminated film and preparation method thereof for flexible electrode |
| CN109368623A (en) * | 2018-09-20 | 2019-02-22 | 苏州博努奇纺织有限公司 | A kind of nano metal intercalated graphite alkene preparation method |
| CN111099583A (en) * | 2018-10-26 | 2020-05-05 | 南京化学工业园环保产业协同创新有限公司 | Efficient composite synthesis method of graphene and nano-silver |
| CN111099583B (en) * | 2018-10-26 | 2022-04-29 | 南京化学工业园环保产业协同创新有限公司 | Efficient composite synthesis method of graphene and nano-silver |
| CN109354011A (en) * | 2018-11-17 | 2019-02-19 | 璧典附 | A kind of environment-friendly preparation method thereof of graphene |
| CN110946148A (en) * | 2019-11-29 | 2020-04-03 | 陕西速源节能科技有限公司 | Preparation method of environment-friendly antibacterial agent |
| CN116671515A (en) * | 2023-04-23 | 2023-09-01 | 合创(广州)科技研究有限公司 | Nano silver antibacterial liquid and application thereof |
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