CN103833004A - Method for preparing water-soluble fluorescent carbon nanoparticle dots - Google Patents
Method for preparing water-soluble fluorescent carbon nanoparticle dots Download PDFInfo
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- CN103833004A CN103833004A CN201410071907.7A CN201410071907A CN103833004A CN 103833004 A CN103833004 A CN 103833004A CN 201410071907 A CN201410071907 A CN 201410071907A CN 103833004 A CN103833004 A CN 103833004A
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Abstract
The invention provides a method for preparing water-soluble fluorescent carbon nanoparticle dots. The method is characterized by comprising the following steps: using a high temperature and high pressure hydrothermal method for treating pentosan which is obtained by using an alkaline process for extracting bleached broad leaf pulp and serves as a raw material, filtering so as to obtain a pale yellow liquid product and a dark brown solid product, wherein the solid product is used as a high-performance adsorbent for adsorption of heavy metal ions Pb (II) and Cd (II), centrifuging the pale yellow liquid product at a high speed, controlling centrifugal rotating speed and time, removing insoluble solids, removing components such as unreacted sugar and salts by using a dialysis bag, and concentrating so as to obtain the water-soluble fluorescent carbon nanoparticle dots. The operation technology has the main characteristics that the pentosan obtained by extracting pulping and papermaking byproducts is used as the raw material and is environmentally friendly, low in cost and easy to obtain, acid-base salts such as passivator do not need to be added during reaction, the product has good water solubility and fluorescent effect, the hydrothermal reaction process is simple to operate, and the cost is low.
Description
Affiliated technical field:
The present invention relates to field of nano material preparation, particularly relate to a kind of method of preparing water-soluble fluorescent carbon nano-particles point.
Background technology:
The annual papermaking annual value of production in the whole world reaches 400,000,000 tons, and the adult timber of annual consumption is ten hundreds of, but practical efficiency is very low, and large content of starting materials becomes waste material abandoned.As the important intermediate of paper technology, bleaching broad-leaved slurry cost is lower and productive rate is very high, and it is rich in abundant hemicellulose mixture simultaneously, comprises ribose, wood sugar, pectinose etc.In actual production process, these piperylenes are removed conventionally after treatment, further obtain high-quality paper, and the piperylene of processing does not have further utilization directly to go out of use, and causes a large amount of wastes.
Fluorescence nanoparticle is because its unique optical property, good electrical properties and good biocompatibility are widely used as metal probe, biomarker, the aspects such as optical sensor.Traditional fluorescent nano particles is mainly semiconductor particle, but in use can discharge Cd, and the heavy metal ion such as Pb make it have compared with large toxicity and are not suitable for scale operation.Metal fluorescent nano particles, for example, gold, Nano silver grain, light stability has overcome poisonous defect by force simultaneously, but cost is higher, is unfavorable for widespread use.
United States Patent (USP) (US7829772B2) has been introduced a kind of under water vapour existence condition, adopts the method for laser ablation powdered graphite, obtains carbon granule of nano-scale, but even if this particle does not have fluorescent effect after acid treatment yet, subsequently with PEG
1500Nbe mixed in 120 ℃ 72 hours, obtain the carbon particles of the size distribution 5～10nm of surface passivation, demonstrate good fluorescent effect.The fluorescent particles fluorescence efficiency 5%～10% that this method obtains, reaction relates to laser ablation, strong nitric acid treatment, passivator passivation, the time is longer, and has increased reaction cost.
United States Patent (USP) (WO021620A1) has been introduced a kind of benzene that directly burns in air, toluene, dimethylbenzene etc. are prepared the method for fluorescence carbon nano-particles containing aromatic solvent, carbon particles presents wider size distribution, be 10～60nm, be dispersed in ethanol, have stronger fluorescence response when excitation wavelength 475nm, quantum yield reaches 12～13%.But water-soluble poor, desired raw material is organic reagent simultaneously, and cost is higher, and carrying capacity of environment is large.
Publication number be CN103011126 Introduction To Cn Patent a kind of preparation technology of water soluble fluorescence charcoal quantum dot, this method is mixed glucose with propanedioic acid two ester, after 140～160 ℃ of backflows, be cooled to room temperature, after 100～120 ℃ of vacuum-drying 2h of product, be dissolved in distilled water, after centrifugation lyophilize, obtain target fluorescent carbon point, particle size were 2～4nm, fluorescence efficiency reaches 24%.Though this method has improved quantum yield, in reaction, the organic solvent of application becomes trunk, and process is more loaded down with trivial details.
Publication number be CN102849724 Introduction To Cn Patent a kind of preparation method of water-soluble carbon quantum dot, the graphite impurities that this method produces when arc process is prepared to Single Walled Carbon Nanotube adds in the aqueous solution containing tensio-active agent and disperses, centrifugal, obtain the narrower graphite granule of size, after reacting with strong oxidizer, neutralize by alkali, dialysis tubing separates and obtains water-soluble carbon quantum dot, although this method obtains the quantum dot of different-grain diameter, but relate to the vitriol oil in reaction, concentrated nitric acid, the strong oxidizers such as potassium permanganate, cause corrosion and the environmental pollution of equipment, be unfavorable for large-scale commercial production.
Publication number be CN102071019 Introduction To Cn Patent a kind of preparation method of the water-soluble carbon nano-particles material with photoluminescent property, the method is using D/W as precursor solution, add after additive, 300W power ultrasonic 4～6 hours, regulates PH to neutral rear recrystallization processing, obtains carbon nano-particles, ultrasonic method is simple to operate, but in reaction, relate to equally hydrochloric acid strong oxidizer, and reaction vessel is had relatively high expectations, increased reaction cost.
Publication number be CN102127431 Introduction To Cn Patent a kind of carbon quantum dot method for making and apply the method that this quantum dot is prepared photocatalyst, this method adds inorganic strong alkali to obtain electrolytic solution after ethanol is mixed according to a certain volume with distilled water to put into electrolyzer, using graphite carbon rod as electrode, at 10～200mA/cm
2current density under carry out electrochemical reaction 2～4h, finally add siccative, obtain carbon quantum dot by column chromatography for separation, this method is carried out two step operations, once electrolytic primary column chromatography separates, reaction is complicated and larger to instrument infringement.
In sum, traditional ionizing radiation, laser ablation, ultrasonic, electrochemical oxidation, the high losses of method such as burning, reaction is complicated, contaminate environment, need the passivator such as strong acid-base, the present invention utilizes hydrothermal method to prepare fluorescent carbon nano-particles, and reaction is take water as solvent, under High Temperature High Pressure, carry out, mild condition, operation of equipment is simple, can reduce temperature of reaction and Reaction time shorten than traditional method, be a kind of quick, easy, method of effectively preparing fluorescent carbon nano-particles, prepared carbon nano-particles fluorescence efficiency is high.
Summary of the invention:
The object of the present invention is to provide a kind of method of preparing water-soluble fluorescent carbon nano-particles point.
In order to achieve the above object, the technical solution used in the present invention comprises: a kind of method of preparing water-soluble fluorescent carbon nano-particles point, it is characterized in that: to bleach piperylene that broad-leaved slurry alkaline process extracts as raw material, after High Temperature High Pressure hydro-thermal method is processed, filter to obtain light yellow liquid product and dark brown solid product, wherein solid product is as high-performance adsorbent Adsorption of Heavy Metal Ions Pb(II) and Cd(II), by light yellow liquid product high speed centrifugation, control centrifugal rotational speed and time, remove insoluble solids, remove the compositions such as unreacted sugar and salt with dialysis tubing, then obtain having water miscible fluorescent carbon nano-particles point through concentrating.
Advantage of the present invention is:
1, starch the piperylene extracting as raw material to bleach broad-leaved, make full use of the by product of papermaking industry, abundant raw material is cheap and easy to get, and piperylene is as the complex body of several five carbon monose, and environmental-friendly natural is pollution-free, and after hydrothermal treatment consists, carbonization degree is higher.
2, the present invention has overcome deficiency of the prior art, has changed traditional production technique, uses hydro-thermal reaction, take water as solvent, raw material does not need pre-treatment, reduces temperature of reaction, Reaction time shorten, reaction conditions gentleness, process operation is simple, and production cost is low, and yield is high.
3, the present invention synchronously obtains solid product and product liquid, the heavy metal ion of solid product in can active adsorption sewage, and product liquid has good fluorescent effect, has increased its market application foreground and economic benefit.
4, in the present invention's reaction, do not add the passivator such as acid-alkali salt, without extra process, environmentally safe, product is water-soluble, shows the susceptibility to PH, does reference material as reference take Quinine Sulphate Di HC, quantum yield can reach 42%.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of water-soluble fluorescent carbon nano-particles point.
embodiment:
Below the invention process is described in further detail:
A kind of method of preparing water-soluble fluorescent carbon nano-particles point, it is characterized in that: to bleach piperylene that broad-leaved slurry alkaline process extracts as raw material, after High Temperature High Pressure hydro-thermal method is processed, filter to obtain light yellow liquid product and dark brown solid product, wherein solid product is as high-performance adsorbent Adsorption of Heavy Metal Ions Pb(II) and Cd(II), by light yellow liquid product high speed centrifugation, control centrifugal rotational speed and time, remove insoluble solids, remove the compositions such as unreacted sugar and salt with dialysis tubing, then obtain having water miscible fluorescent carbon nano-particles point through concentrating.
Below, the present invention will be further detailed with embodiment, but it is not limited to any or the similar example of these embodiment.
Embodiment 1:
The bleaching broad-leaved slurry of 20g brightness 88% adds 1.5mol/L KOH solution 250ml, under room temperature, stir and extract 30 hours, filter, filtrate regulates PH to 2～3 with 2mol/L HCl, add ethanol to make solid precipitation, the volume of ethanol is liquid volume 3 times, precipitation is cleaned after filtration to neutrality, obtain piperylene, productive rate is 12.5%.
It is 5% the aqueous solution that the piperylene of extraction is mixed with to concentration, put into tetrafluoroethylene in reactor, guarantee that liquor capacity and still volume are 7:8,10 ℃/min temperature rise rate is warming up to 190 ℃ of target temperatures, constant temperature 8h, the cooling room temperature of being down to, filter, the weak yellow liquid that collection obtains, with the rotating speed centrifugation twice of 12000r/min, removes throw out, the dialysis tubing dialysis that liquid is 2000 with interception 3 days, remove macromole product, after concentrating, obtain water-soluble fluorescent carbon nano dot, particle size range is at 10～50nm(accompanying drawing 1).
The brown solid that filtration is obtained distilled water for product, 95% absolute ethanol washing are limpid to filtrate, 80 ℃ of oven for drying, the solid product obtaining is the globosity of particle diameter 150～1200nm, surface is containing 39.1 carboxyl functional group, and under room temperature, test is to Pb(II) and Cd(II) saturated adsorption value be respectively 380.1mg/g and 100.8mg/g.
Embodiment 2:
The bleaching broad-leaved slurry of 20g brightness 88% adds 3mol/L KOH solution 250ml, under room temperature, stir and extract 25 hours, filter, filtrate regulates PH to 2～3 with 2mol/L HCl, add ethanol to make solid precipitation, the volume of ethanol is liquid volume 3 times, precipitation is cleaned after filtration to neutrality, obtain piperylene, productive rate is 14%.
It is 7% the aqueous solution that the piperylene of extraction is mixed with to concentration, put into tetrafluoroethylene in reactor, guarantee that liquor capacity and still volume are 9:10,10 ℃/min temperature rise rate is warming up to 240 ℃ of target temperatures, constant temperature 10h, the cooling room temperature of being down to, filter, the weak yellow liquid that collection obtains, with the rotating speed centrifugation twice of 11000r/min, removes throw out, the dialysis tubing dialysis that liquid is 3000 with interception 3 days, remove macromole product, after concentrating, obtain water-soluble fluorescent carbon nano dot, particle size range is at 20～40nm.
The brown solid that filtration is obtained distilled water for product, 95% absolute ethanol washing are limpid to filtrate, 80 ℃ of oven for drying, the solid product obtaining is the globosity of particle diameter 300～900nm, surface is containing 36.5 carboxyl functional group, and under room temperature, test is to Pb(II) and Cd(II) saturated adsorption value be respectively 353.1mg/g and 94.8mg/g.
Claims (8)
1. prepare the method for water-soluble fluorescent carbon nano-particles point for one kind, it is characterized in that: to bleach piperylene that broad-leaved slurry alkaline process extracts as raw material, after High Temperature High Pressure hydro-thermal method is processed, filter to obtain light yellow liquid product and dark brown solid product, wherein solid product is as high-performance adsorbent Adsorption of Heavy Metal Ions Pb(II) and Cd(II), by light yellow liquid product high speed centrifugation, control centrifugal rotational speed and time, remove insoluble solids, remove the compositions such as unreacted sugar and salt with dialysis tubing, then obtain having water miscible fluorescent carbon nano-particles point through concentrating.
2. according to a kind of method of preparing water-soluble fluorescent carbon nano-particles point claimed in claim 1, it is characterized in that: the highly basic that alkaline process extracts piperylene employing is NaOH or KOH, and concentration of lye is 1.0～3.0mol/L, alkaline process extraction time is 15～30 hours.
3. according to a kind of method of preparing water-soluble fluorescent carbon nano-particles point claimed in claim 1, it is characterized in that: hydrothermal temperature is at 190～240 ℃, and the reaction times is 8～12 hours.
4. according to a kind of method of preparing water-soluble fluorescent carbon nano-particles point claimed in claim 1, it is characterized in that: the light yellow liquid product centrifugation rate of gained is 8000～15000rpm, and centrifugation time is min.
5. according to a kind of method of preparing water-soluble fluorescent carbon nano-particles point claimed in claim 1, it is characterized in that: hydro-thermal reaction material concentration is 2.5%～12.5%, solvent capacity is 9:10～3:5 with reaction capacity ratio.
6. according to a kind of method of preparing water-soluble fluorescent carbon nano-particles point claimed in claim 1, it is characterized in that: the molecular interception amount of dialysis tubing is 1000～5000.
7. according to a kind of method of preparing water-soluble fluorescent carbon nano-particles point claimed in claim 1, it is characterized in that: the fluorescence efficiency of the prepared water-soluble carbon nanoparticle point of hydrothermal method is 42.5%.
8. according to a kind of method of preparing water-soluble fluorescent carbon nano-particles point claimed in claim 1, it is characterized in that: the particle diameter of the prepared water-soluble carbon nanoparticle point of hydrothermal method is 10～40nm.
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| CN1431231A (en) * | 2003-01-29 | 2003-07-23 | 广西壮族自治区中国科学院广西植物研究所 | Method for extracting xylan from woody fiber material |
| US20100215760A1 (en) * | 2007-10-03 | 2010-08-26 | Jawaharlal Nehru Centre For Advanced Scientific Research | Intrinscially fluorescent carbon nanospheres and a process thereof |
| CN102071018A (en) * | 2010-12-24 | 2011-05-25 | 苏州方昇光电装备技术有限公司 | Method for preparing magnetic fluorescent nanocomposite material |
| CN103265952A (en) * | 2013-05-22 | 2013-08-28 | 湖南师范大学 | Environmental-friendly synthesis method of fluorescent carbon dot with up-down conversion function |
| CN103342347A (en) * | 2013-05-09 | 2013-10-09 | 江苏大学 | Preparation method of carbon quantum dots with high fluorescence property |
| CN103361047A (en) * | 2012-03-28 | 2013-10-23 | 中国科学院大连化学物理研究所 | Functional fluorescence carbon nanoparticles based on natural saccharide materials and preparation method and application thereof |
| CN103588190A (en) * | 2013-10-31 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparation of carbon microsphere from lignocellulose |
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- 2014-02-28 CN CN201410071907.7A patent/CN103833004A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431231A (en) * | 2003-01-29 | 2003-07-23 | 广西壮族自治区中国科学院广西植物研究所 | Method for extracting xylan from woody fiber material |
| US20100215760A1 (en) * | 2007-10-03 | 2010-08-26 | Jawaharlal Nehru Centre For Advanced Scientific Research | Intrinscially fluorescent carbon nanospheres and a process thereof |
| CN102071018A (en) * | 2010-12-24 | 2011-05-25 | 苏州方昇光电装备技术有限公司 | Method for preparing magnetic fluorescent nanocomposite material |
| CN103361047A (en) * | 2012-03-28 | 2013-10-23 | 中国科学院大连化学物理研究所 | Functional fluorescence carbon nanoparticles based on natural saccharide materials and preparation method and application thereof |
| CN103342347A (en) * | 2013-05-09 | 2013-10-09 | 江苏大学 | Preparation method of carbon quantum dots with high fluorescence property |
| CN103265952A (en) * | 2013-05-22 | 2013-08-28 | 湖南师范大学 | Environmental-friendly synthesis method of fluorescent carbon dot with up-down conversion function |
| CN103588190A (en) * | 2013-10-31 | 2014-02-19 | 中国科学院过程工程研究所 | Method for preparation of carbon microsphere from lignocellulose |
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Application publication date: 20140604 |