CN102849722B - Carbon nano-dot, and preparation method and application thereof - Google Patents
Carbon nano-dot, and preparation method and application thereof Download PDFInfo
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- CN102849722B CN102849722B CN201210312844.0A CN201210312844A CN102849722B CN 102849722 B CN102849722 B CN 102849722B CN 201210312844 A CN201210312844 A CN 201210312844A CN 102849722 B CN102849722 B CN 102849722B
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Abstract
The invention discloses a carbon nano-dot, and a preparation method and an application thereof, and solves a problem that the application of present nano-dots is restricted because of high preparation cost and easy fluorescent quenching appearance of an aggregate state. According to the invention, the carbon nano-dot having a high fluorescence quantum efficiency is prepared through adopting a polycarboxyl or polyhydroxy contained organic compound, or an amino acid as a raw material, and urea as a surface passivation modification agent, and through a microwave process, and a carbon nano-dot fluorescent ink is prepared through using the carbon nano-dot. The preparation method disclosed in the invention has the advantages of simplicity, low cost and convenient large-scale production; the fluorescent quenching of the prepared carbon nano-dot on the surface of a biological product does not appear, and the highest fluorescence quantum efficiency is 42%; and the prepared carbon nano-dot fluorescent ink is nontoxic, does not generate a precipitate after long-time dispose, and can be applied to the biological imaging field, the biological product identification field, the information storage field, the information encryption field, the false proof field, the illumination display field, the photovoltaic device field and the like.
Description
Technical field
The present invention relates to a kind of carbon nano dot and preparation method thereof and application, belong to nanometer material science field.
Background technology
Carbon nano dot is a kind of novel nano material, because it has advantages of many uniquenesses (as chemical stability, without optical flare, fast lightly float, nontoxic, excellent biocompatibility) and be subject to increasing concern (Luminescent Carbon Nanodots:Emergent Nanolights, Sheila N. Baker, Gary A. Baker, Angew. Chem. Int. Ed., 2010,49,6726).The carbon nano dot with fluorescent characteristic has potential application in fields such as bio-imaging, laser, photoelectric devices.
Carbon nano dot can be prepared by several different methods, as laser ablation, electrochemical process, arc discharge method, pyrolysis method, excusing from death and microwave method.In these methods, microwave method is because cost is low, relative environmental protection is had an high regard for.Microwave method can improve rapidly the temperature of reactant, and fast reaction speed and pyrolysis rate can be realized the effect of pyrolysis method and significantly shorten preparation time.Pyrolysis method and microwave method are prepared carbon nano dot conventionally to contain many carboxyls or polyhydric organic compound as starting material, for example, document (Microwave synthesis of fluorescent carbon nanoparticles with electrochemiluminescence properties, Hui Zhu, Xiaolei Wang, Yali Li, Zhongjun Wang, Fan Yang, Xiurong Yang, Chem. Commun., 2009,51),, taking the carbohydrate derivative such as glucose and fructose as raw material, prepare carbon nano dot by microwave method; Document (Microwave assisted one-step green synthesis of cell-permeable multicolor photoluminescent carbon dots without surface passivation reagents, Xiaohui Wang, Konggang Qu, Bailu Xu, Jinsong Ren, Xiaogang Qu, J. Mater. Chem., 2011,21,244),, taking glycerine as raw material, prepare carbon nano dot by microwave method; Document (Tuning of photoluminescence on different surface functionalized carbon quantum dots, Sourov Chandra, Shaheen H. Pathan, Shouvik Mitra, Binita H. Modha, Arunava Goswami, Panchanan Pramanik, RSC Adv., 2012,2,3602), taking chitosan, Lalgine and starch as raw material, prepare carbon nano dot by microwave method.
In order to obtain the carbon nano dot with fluorescent characteristic, conventionally need to introduce the surface passivation modifier that contains polymer chain.For example, document (Microwave synthesis of fluorescent carbon nanoparticles with electrochemiluminescence properties, Hui Zhu, Xiaolei Wang, Yali Li, Zhongjun Wang, Fan Yang, Xiurong Yang, Chem. Commun., 2009, 51), taking the carbohydrate derivative such as glucose and fructose as raw material, without surface passivation modifier in the situation that, the carbon nano dot of preparing by microwave method shows very weak fluorescence, after adding polyoxyethylene glycol (molecular-weight average 200) as surface passivation modifier, the carbon nano dot of preparing by microwave method shows the fluorescent appear of enhancing, fluorescence quantum efficiency 3%-6%.But the cost of the surface passivation modifier that contains polymer chain is higher, and the residual surface passivation modifier that contains polymer chain is difficult for removing.The dispersing characteristic that carbon nano dot can have at dilute solution state, the dilute solution of the carbon nano dot of surface passivation can show compared with strong fluorescent properties.And under state of aggregation, material nano dimensional effect disappears, can show strong fluorescent quenching phenomenon, greatly limit the application of such material in solid luminescent system.In prior art, also do not have that preparation cost is low simultaneously, preparation method is simple, environmental protection, in solid-state system, show high-fluorescence quantum yield, and can be applied to the carbon nano dot in daily life.
Summary of the invention
The object of the invention is to reduce the preparation cost of fluorescent carbon nano dot, widen the Application Areas of carbon nano dot, a kind of carbon nano dot and preparation method thereof and application are provided.
The invention provides a kind of carbon nano dot, this carbon nano dot is to contain many carboxyls or polyhydric organic compound as raw material, or taking amino acid as raw material, is prepared from taking urea as surface passivation agent, and step is as follows:
1. urea with containing many carboxyls or polyhydric organic compound, or amino acid in mass ratio 0.1:1-4:1 be mixed with the aqueous solution;
2. the 1. prepared aqueous solution is reacted and obtained brownish black solid by microwave heating;
3. by brownish black solid through heating under vacuum, remove residual micromolecular compound, obtain carbon nano dot.
Preferably, described many carboxyls or polyhydric organic compound are citric acid, ethylenediamine tetraacetic acid (EDTA), glycerine, glucose, fructose, sucrose, chitosan or starch; More preferably, citric acid, glycerine, glucose or sucrose; Most preferably citric acid.
Preferably, described amino acid is glycine or L-glutamic acid; More preferably, glycine.
Preferably, step 1. in, described urea with containing many carboxyls or polyhydric organic compound, or amino acid in mass ratio 0.1:1-4:1 be mixed with saturated aqueous solution.
Preferably, step 2. in, the described aqueous solution is through 500-900W power microwave heating 3-10 minute, more preferably through 700W power microwave heating 4 minutes.
Preferably, step 3. in, the vacuum tightness of described heating under vacuum is 0.001-0.1 handkerchief, Heating temperature is 50-70 degree Celsius, heat-up time 1-2 hour; More preferably, the vacuum tightness of described heating under vacuum is 0.01 handkerchief, and Heating temperature is 60 degrees Celsius, 1 hour heat-up time.
The preparation method who the invention provides a kind of carbon nano dot, comprises the following steps:
1. urea with containing many carboxyls or polyhydric organic compound, or amino acid 0.1:1-4:1 obtained aqueous solution in mass ratio;
2. the 1. prepared aqueous solution is reacted and obtained brownish black solid by microwave heating;
3. by brownish black solid through heating under vacuum, remove residual micromolecular compound, obtain carbon nano dot.
The present invention also provides a kind of carbon nano dot in the application of preparing in fluorescent ink, is by soluble in water carbon nano dot, through centrifugal, obtains supernatant liquor; The supernatant liquor obtaining, through water or organic solvent diluting, is obtained to carbon nano dot fluorescent ink.
Preferably, described organic solvent is ethanol.
Preferably, centrifugal rotational speed is 2000-4000 rev/min, and the time is 15-30 minute; More preferably, centrifugal rotational speed is 3000 revs/min, and the time is 20 minutes.
Beneficial effect of the present invention:
(1) the present invention is to contain many carboxyls or polyhydric organic compound, or amino acid is raw material, using urea as surface passivation modifier, prepare the carbon nano dot of high fluorescence quantum efficiency by microwave method, overcome prior art using polymer chain is high as surface passivation modifier preparation cost, quenching of fluorescence easily occurs state of aggregation problem, preparation method of the present invention is simple, and cost is low, is convenient to scale operation;
(2) the prepared carbon nano dot maximum fluorescence quantum yield of the present invention can be up to being 42%;
(3) abundant amide group and carboxyl are contained in the prepared carbon nano dot surface of the present invention, there is excellent biocompatibility, can effectively disperse to be attached to the solid-state biological product surfaces such as paper, vegetable fibre, fur, avoid carbon nano dot to reunite, retain the strong fluorescence emitting characteristics of carbon nano dot, its fluorescence emission peak depends on excitation wavelength; The carbon nano dot of preparation is attached to inorganic materials, plastics, man-made fiber surface, and carbon nano dot is reunited, and its fluorescent emission great Fu temper goes out, and according to this characteristic, carbon nano dot of the present invention can be used as the appraisal basis of biological product;
(4) the prepared carbon nano dot fluorescent ink of the present invention is nontoxic, permanent placement can not produce precipitation, there is strong fluorescent characteristic, mark fluorescent graphic on skin safely, may be used on the multiple fields such as bio-imaging, biological product qualification, information storage, information encryption, false proof, illumination demonstration, photovoltaic device.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the carbon nano dot of the embodiment of the present invention 1;
Fig. 2 be in the atomic power scanned picture of carbon nano dot of the embodiment of the present invention 1 and atomic power scanned picture A to the altitude curve of B position;
Fig. 3 is the infrared spectrogram of the carbon nano dot of the embodiment of the present invention 1;
Fig. 4 is the ultra-violet absorption spectrum of the aqueous solution of the carbon nano dot of the embodiment of the present invention 12 and the fluorescence emission spectrogram under different excitation wavelengths;
Fig. 5 is that the carbon nano dot fluorescent ink of the embodiment of the present invention 12 drips on filter paper, after air drying, and the fluorescence emission spectral curve under different excitation wavelengths;
Fig. 6 is that the carbon nano dot fluorescent ink of the embodiment of the present invention 12 makes growth of mung beans become to have the photo under different-waveband illumination of the bean sprouts of fluorescent characteristic;
Fig. 7 is the fluorescence spectrum figure of the urine of big white mouse while drinking the carbon nano dot fluorescent ink one month of the embodiment of the present invention 12 under different excitation wavelengths;
Fig. 8 is the carbon nano dot fluorescent ink after month that big white mouse is drunk the embodiment of the present invention 12, stops drinking carbon nano dot fluorescent ink, changes urine while drinking normal tap water 1 month fluorescence spectrum figure under different excitation wavelengths;
Fig. 9 is the fluorescence spectrum figure of urine under different excitation wavelengths that big white mouse is drunk normal tap water;
Figure 10 is the carbon nano dot fluorescent ink and the fluorescence photo that is purchased green fluorescence pen and forms enciphered digital on paper of the embodiment of the present invention 12;
Figure 11 is the cotton thread and the photo of nylon fiber under different excitation wavelengths of being infected with and not being infected with the carbon nano dot fluorescent ink of the embodiment of the present invention 12;
Figure 12 uses fingerprint trace that the carbon nano dot fluorescent ink of the embodiment of the present invention 12 stays on the paper photo under different excitation wavelengths;
Figure 13 is the fluorescence photo that the carbon nano dot fluorescent ink of the embodiment of the present invention 12 leaves fluorescent graphic on skin;
Figure 14 is the ethanolic soln of carbon nano dot of the embodiment of the present invention 13 fluorescence emission spectrogram under different excitation wavelengths;
Figure 15 is the aqueous solution of carbon nano dot of the embodiment of the present invention 14 fluorescence emission spectrogram under different excitation wavelengths;
Figure 16 is that the carbon nano dot fluorescent ink of the embodiment of the present invention 14 drips on filter paper, after dry air, and the fluorescence emission spectral curve under different excitation wavelengths;
Figure 17 is the ethanolic soln of carbon nano dot of the embodiment of the present invention 15 fluorescence emission spectrogram under different excitation wavelengths;
Figure 18 is the aqueous solution of carbon nano dot of the embodiment of the present invention 16 fluorescence emission spectrogram under different excitation wavelengths;
Figure 19 is the aqueous solution of carbon nano dot of the embodiment of the present invention 17 fluorescence emission spectrogram under different excitation wavelengths;
Figure 20 is that the carbon nano dot fluorescent ink of the embodiment of the present invention 17 drips on filter paper, after air drying, and the fluorescence emission spectral curve under different excitation wavelengths;
Figure 21 is the ethanolic soln of carbon nano dot of the embodiment of the present invention 18 fluorescence emission spectrogram under different excitation wavelengths;
Figure 22 is the aqueous solution of carbon nano dot of the embodiment of the present invention 19 fluorescence emission spectrogram under different excitation wavelengths;
Figure 23 is the aqueous solution of carbon nano dot of the embodiment of the present invention 20 fluorescence emission spectrogram under different excitation wavelengths;
Figure 24 is the aqueous solution of carbon nano dot of the embodiment of the present invention 21 fluorescence emission spectrogram under different excitation wavelengths;
Figure 25 is the aqueous solution of carbon nano dot of the embodiment of the present invention 22 fluorescence emission spectrogram under different excitation wavelengths.
Embodiment
The invention provides a kind of carbon nano dot, this carbon nano dot is to contain many carboxyls or polyhydric organic compound as raw material, or taking amino acid as raw material, is prepared from taking urea as surface passivation agent, and step is as follows:
1. urea with containing many carboxyls or polyhydric organic compound, or amino acid 0.1:1-4:1 obtained aqueous solution in mass ratio;
2. the 1. prepared aqueous solution is reacted and obtained brownish black solid by microwave heating;
3. the brownish black solid of preparation, through heating under vacuum, is removed residual micromolecular compound, obtains carbon nano dot.
The performance of carbon nano dot prepared by the present invention, depends on the mass ratio relation of raw material and selected raw material and the urea of preparing carbon nano dot; When urea with containing many carboxyls or polyhydric organic compound, or amino acid in mass ratio 0.1:1-4:1 be mixed with saturated aqueous solution, the performance of the carbon nano dot of preparation is better; As long as containing many carboxyls or polyhydric organic compound, or amino acid all can be used as raw material of the present invention and prepares carbon nano dot; Urea does not limit, and is purchased.
Preferably, described is citric acid, ethylenediamine tetraacetic acid (EDTA), glycerine, glucose, fructose, sucrose, chitosan or starch containing many carboxyls or polyhydric organic compound; More preferably, citric acid, glycerine, glucose or sucrose; Most preferably citric acid.
Preferably, described amino acid is glycine or L-glutamic acid; More preferably, glycine.
The microwave heating of step of the present invention in is 2. technology well known in the art, preferably, the aqueous solution is 1. put into microwave oven, through 500-900W power microwave heating 3-10 minute; More preferably through 700W power microwave heating 4 minutes.
Preferably, step 3. in, the vacuum tightness of described heating under vacuum is 0.001-0.1 handkerchief, Heating temperature is 50-70 degree Celsius, heat-up time 1-2 hour; More preferably, the vacuum tightness of described heating under vacuum is 0.01 handkerchief, and Heating temperature is 60 degrees Celsius, 1 hour heat-up time.
The micromolecular compound that 3. step of the present invention removes is mainly residual urea.
The preparation method who the invention provides a kind of carbon nano dot, comprises the following steps:
1. urea with containing many carboxyls or polyhydric organic compound, or amino acid in mass ratio 0.1:1-4:1 be mixed with the aqueous solution;
2. the 1. prepared aqueous solution is reacted and obtained brownish black solid by microwave heating;
3. prepare brownish black solid through heating under vacuum, remove residual micromolecular compound, obtain carbon nano dot.
The present invention also provides a kind of carbon nano dot in the application of preparing in fluorescent ink, is by water-soluble carbon nano dot or organic solvent, through centrifugal, obtains supernatant liquor; The supernatant liquor obtaining, through water or organic solvent diluting, is obtained to carbon nano dot fluorescent ink.
Preferably, described organic solvent is ethanol.
Preferably, centrifugal rotational speed is 2000-4000 rev/min, and the time is 15-30 minute; More preferably, centrifugal rotational speed is 3000 revs/min, and the time is 20 minutes.
Further illustrate the present invention below in conjunction with embodiment, in embodiment, use material to pass through commercially available.
Embodiment 1-11 is the Preparation Example of carbon nano dot of the present invention.
Embodiment 1
In conjunction with Fig. 1-3 explanation embodiment 1
The preparation of carbon nano dot of the present invention:
1. 3 grams of urea and 3 grams of citric acids are dissolved in 10 ml waters;
2. 1. prepared urea and lemon aqueous acid are placed in microwave oven, through 700W power microwave heating 4 minutes, obtain brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.01 handkerchief, and temperature is 60 degrees Celsius, heats 1 hour, removes residual micromolecular compound, obtains carbon nano dot.
Fig. 1 is the transmission electron microscope picture of the carbon nano dot of the embodiment of the present invention 1.
Fig. 2 be in the atomic power scanned picture a of carbon nano dot of the embodiment of the present invention 1 and atomic power scanned picture A to the altitude curve b of B position.
Fig. 3 is the infrared spectrogram that sees through of the carbon nano dot of the embodiment of the present invention 1; At 3100-3500 cm
-1the absorption band at place is the absorption vibrational band of ν (O-H) and ν (N-H), 1600-1770 cm
-1for the absorption vibrational band of ν (C=O), show that prepared carbon nano dot surface contains abundant amide group and carboxyl.
Embodiment 2
The preparation of carbon nano dot of the present invention:
1. 3 grams of urea and 3 grams of citric acids are dissolved in 10 ml waters;
2. 1. prepared urea and lemon aqueous acid are placed in microwave oven, through 500W power microwave heating 10 minutes, obtain brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.01 handkerchief, and temperature is 60 degrees Celsius, heats 1 hour, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 3
The preparation of carbon nano dot of the present invention:
1. 0.3 gram of urea and 3 grams of citric acids are dissolved in 10 ml waters;
2. 1. prepared urea and lemon aqueous acid are placed in microwave oven, through 700W power microwave heating 4 minutes, obtain brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.01 handkerchief, and temperature is 50 degrees Celsius, heats 2 hours, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 4
The preparation of carbon nano dot of the present invention:
1. 0.3 gram of urea and 3 grams of citric acids are dissolved in 10 ml waters;
2. 1. prepared urea and lemon aqueous acid are placed in microwave oven, through 700W power microwave heating 4 minutes, obtain brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.001 handkerchief, and temperature is 60 degrees Celsius, heats 1 hour, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 5
The preparation of carbon nano dot of the present invention:
1. 6 grams of urea and 3 grams of citric acids are dissolved in 10 ml waters;
2. 1. prepared urea and lemon aqueous acid are placed in microwave oven, through 900W power microwave heating 3 minutes, obtain brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.01 handkerchief, and temperature is 55 degrees Celsius, heats 2 hours, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 6
The preparation of carbon nano dot of the present invention:
1. 12 grams of urea and 3 grams of citric acids are dissolved in 15 ml waters;
2. 1. prepared urea and lemon aqueous acid are placed in microwave oven, through 700W power microwave heating 5 minutes, obtain brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.01 handkerchief, and temperature is 70 degrees Celsius, heats 1 hour, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 7
The preparation of carbon nano dot of the present invention:
1. 12 grams of urea and 3 grams of citric acids are dissolved in 10 ml waters;
2. 1. prepared urea and lemon aqueous acid are placed in microwave oven, through 500W power microwave heating 9 minutes, obtain brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.1 handkerchief, and temperature is 60 degrees Celsius, heats 1 hour, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 8
The preparation of carbon nano dot of the present invention:
1. 3 grams of urea and 3 grams of glycerine are dissolved in 12 ml waters;
2. the aqueous solution of 1. prepared urea and glycerine is placed in microwave oven, through 600W power microwave heating 8 minutes, obtains brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.05 handkerchief, and temperature is 55 degrees Celsius, heats 2 hours, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 9
The preparation of carbon nano dot of the present invention:
1. 3 grams of urea and 3 grams of glucose are dissolved in 12 ml waters;
2. the aqueous solution of 1. prepared urea and glucose is placed in microwave oven, through 600W power microwave heating 8 minutes, obtains brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.01 handkerchief, and temperature is 60 degrees Celsius, heats 1 hour, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 10
The preparation of carbon nano dot of the present invention:
1. 3 grams of urea and 3 grams of sucrose dissolved are in 15 ml waters;
2. the aqueous solution of 1. prepared urea and sucrose is placed in microwave oven, through 700W power microwave heating 6 minutes, obtains brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.01 handkerchief, and temperature is 70 degrees Celsius, heats 1 hour, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 11
The preparation of carbon nano dot of the present invention:
1. 3 grams of urea and 3 grams of glycine are dissolved in 10 ml waters;
2. the aqueous solution of 1. prepared urea and glycine is placed in microwave oven, through 700W power microwave heating 7 minutes, obtains brownish black solid;
3. the brownish black solid of preparation is placed in vacuum drying oven, vacuum tightness is 0.01 handkerchief, and temperature is 60 degrees Celsius, heats 2 hours, removes residual micromolecular compound, obtains carbon nano dot.
Embodiment 12-22 is that carbon nano dot of the present invention is in the Application Example of preparing in fluorescent ink.
Embodiment 12
In conjunction with Fig. 4-13 explanation the present embodiment
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 1 is obtained is dissolved in 100 ml waters, and through centrifugal treating, 3000 revs/min of centrifugal rotational speeds, centrifugation time 20 minutes, obtains supernatant liquor; The supernatant liquor obtaining dilutes through water, and obtaining concentration is the aqueous solution of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
The prepared permanent placement of carbon nano dot fluorescent ink can not produce precipitation.
Fig. 4 is the ultra-violet absorption spectrum of the aqueous solution of the carbon nano dot of the embodiment of the present invention 12 and the fluorescence emission spectrogram under different excitation wavelengths: curve 1 is uv absorption spectra, curve 2 is the fluorescence emission spectrogram of 340nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 420nm under exciting, curve 5 is the fluorescence emission spectrogram of 460nm under exciting, and curve 6 is the fluorescence emission spectrogram of 500nm under exciting; Excitation wavelength is that hyperfluorescenceZeng Yongminggaoyingguang emission peak 540nm appears in 420nm as can be seen from Figure 1, and maximum fluorescence quantum yield is 14%.
Fig. 5 is that the carbon nano dot fluorescent ink of the embodiment of the present invention 12 drips on filter paper, after air drying, fluorescence emission spectral curve under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 340nm under exciting, curve 2 is the fluorescence emission spectrogram of 380nm under exciting, curve 3 is the fluorescence emission spectrogram of 420nm under exciting, curve 4 is the fluorescence emission spectrogram of 460nm under exciting, and curve 5 is the fluorescence emission spectrogram of 500nm under exciting; Excitation wavelength is that hyperfluorescenceZeng Yongminggaoyingguang emission peak 515nm appears in 420nm as can be seen from Figure 2, and maximum fluorescence quantum yield is 40%.
Fig. 6 is that the carbon nano dot fluorescent ink of the embodiment of the present invention 12 makes growth of mung beans become to have the photo under different-waveband illumination of the bean sprouts of fluorescent characteristic: (a) photo under natural light, (b) excitation wavelength 340 nm, receive the fluorescence photo that wavelength is greater than 395 nm light, it is blue that bean sprouts is, (c) excitation wavelength 420 nm, receive the fluorescence photo that wavelength is greater than 450 nm, it is green that bean sprouts is, (d) excitation wavelength 500 nm, receive the fluorescence photo that wavelength is greater than 550 nm, it is orange that bean sprouts is; Show with carbon nano dot fluorescent ink of the present invention nontoxicly to plant, and can dye to plant living body.
Fig. 7 is the fluorescence spectrum figure of the urine of big white mouse while drinking the carbon nano dot fluorescent ink one month of the embodiment of the present invention 12 under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 340nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 400nm under exciting, curve 5 is the fluorescence emission spectrogram of 420nm under exciting, curve 6 is the fluorescence emission spectrogram of 460nm under exciting, curve 7 is the fluorescence emission spectrogram of 480nm under exciting, curve 8 is the fluorescence emission spectrogram of 500nm under exciting, the fluorescent band that 500-600 nm place occurs shows to contain in urine the prepared carbon nano dot of the present invention.
Fig. 8 is the carbon nano dot fluorescent ink after month that big white mouse is drunk the embodiment of the present invention 12, stop drinking carbon nano dot fluorescent ink of the present invention, change urine while drinking normal tap water 1 month fluorescence spectrum figure under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 340nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 400nm under exciting, curve 5 is the fluorescence emission spectrogram of 420nm under exciting, curve 6 is the fluorescence emission spectrogram of 460nm under exciting, the fluorescent band that 500-600 nm place occurs disappears.
Fig. 9 is that big white mouse is drunk the urine of normal tap water (not drinking carbon nano dot fluorescent ink of the present invention) at the fluorescence spectrum figure of different excitation wavelengths: the fluorescence emission spectrogram under curve 1 excites for 340nm, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 400nm under exciting, curve 5 is the fluorescence emission spectrogram of 420nm under exciting, and curve 6 is the fluorescence emission spectrogram of 460nm under exciting.
Fig. 7-9 show, the big white mouse long-term drinking carbon nano dot fluorescent ink of preparing with citric acid and urea of the present invention can not cause death or produce unusual phenomenon, and carbon nano dot fluorescent ink of the present invention can be discharged through urine, nontoxic to animal.
Figure 10 is the fluorescence photo that the carbon nano dot fluorescent ink of the embodiment of the present invention 12 and commercial green fluorescence pen (being purchased) form enciphered digital on paper: on paper, write " 395 " with carbon nano dot fluorescent ink, do not smear and do not write place with carbon nano dot fluorescent ink to be purchased green fluorescence pen again, " 395 " are mended into numeral " 888 "; A figure, excitation wavelength 450-480 nm, receives the light that wavelength is greater than 515 nm, 50 milliseconds of time shutter; B figure, excitation wavelength 510-550 nm, receives the light that wavelength is greater than 590 nm, 150 milliseconds of time shutter; Can find out that a figure shows what show for green 888, b figure be redness 395, show that carbon nano dot fluorescent ink of the present invention can both manifest under different excitation wavelengths, can be used for enciphered digital.
Figure 11 is the cotton thread and the photo of nylon fiber under different excitation wavelengths of being infected with and not being infected with the carbon nano dot fluorescent ink of the embodiment of the present invention 12: cotton thread and the nylon fiber of not being infected with the carbon nano dot fluorescent ink of the embodiment of the present invention 12, (a) optical photograph, (b) excitation wavelength 450-480 nm, receive the fluorescence photo that wavelength is greater than 515 nm light, 50 milliseconds of time shutter, (c) excitation wavelength 510-550 nm, receive the fluorescence photo that wavelength is greater than 590 nm light, 150 milliseconds of time shutter; Be infected with the carbon nano dot fluorescent ink of the embodiment of the present invention 12, and cotton thread after air drying and (d) optical photograph of nylon fiber, (e) excitation wavelength 450-480 nm, receive the fluorescence photo that wavelength is greater than 515 nm, 50 milliseconds of time shutter, can find out that cotton fibre is green, (f) excitation wavelength 510-550 nm, receive the fluorescence photo that wavelength is greater than 590 nm light, 150 milliseconds of time shutter, can find out that cotton fibre takes on a red color; As can be seen from Figure 11, the cotton fibre of being infected with the carbon nano dot fluorescent ink of the embodiment of the present invention 12 shows the fluorescence phenomenon that strong excitation wavelength relies on, and the nylon fiber of being infected with the carbon nano dot fluorescent ink of the embodiment of the present invention 12 does not have fluorescence phenomenon, show that carbon nano dot fluorescent ink of the present invention can identify biological product and Chemicals effectively.
Figure 12 is the carbon nano dot fluorescent ink fingerprints mark photo under different excitation wavelengths on paper that uses the embodiment of the present invention 12, (a) optical photograph, (b) excitation wavelength 340 nm, receive the fluorescence photo that wavelength is greater than 395 nm light, can find out that (b) figure manifests blue fingerprint, (c) excitation wavelength 420 nm, receive the fluorescence photo that wavelength is greater than 450 nm light, can find out (c) figure shows green fingerprint; The fingerprint obtaining can be preserved for a long time.
Figure 13 is the fluorescence photo that the carbon nano dot fluorescent ink of the embodiment of the present invention 12 leaves fluorescent graphic on skin.
Embodiment 13
In conjunction with Figure 14, embodiment 13 is described
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 2 is obtained is dissolved in 200 milliliters of ethanol, and through centrifugal treating, 3000 revs/min of centrifugal rotational speeds, centrifugation time 20 minutes, obtains supernatant liquor; The supernatant liquor obtaining is through alcohol dilution, and obtaining concentration is the ethanolic soln of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 14 is the ethanolic soln of carbon nano dot of the embodiment of the present invention 13 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 340nm under exciting, curve 2 is the fluorescence emission spectrogram of 380nm under exciting, curve 3 is the fluorescence emission spectrogram of 420nm under exciting, curve 4 is the fluorescence emission spectrogram of 460nm under exciting, and curve 5 is the fluorescence emission spectrogram of 500nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 520nm (excitation wavelength 420nm), maximum fluorescence quantum yield is 38%.
Embodiment 14
In conjunction with Figure 15,16 explanation embodiment 14
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 3 is obtained is dissolved in 100 ml waters, and through centrifugal treating, 2000 revs/min of centrifugal rotational speeds, centrifugation time 30 minutes, obtains supernatant liquor; The supernatant liquor obtaining dilutes through water, and obtaining concentration is the aqueous solution of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 15 is the aqueous solution of carbon nano dot of the embodiment of the present invention 14 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 320nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 390nm under exciting, curve 5 is the fluorescence emission spectrogram of 400nm under exciting, and curve 6 is the fluorescence emission spectrogram of 460nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 445nm (excitation wavelength 360nm) maximum fluorescence quantum yield is 18%.
Figure 16 is that the carbon nano dot fluorescent ink of the embodiment of the present invention 14 drips on filter paper, and after air drying, fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 320nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 400nm under exciting, curve 5 is the fluorescence emission spectrogram of 420nm under exciting, and curve 6 is the fluorescence emission spectrogram of 480nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 443nm (excitation wavelength 360nm), maximum fluorescence quantum yield is 18%.
Embodiment 15
In conjunction with Figure 17, embodiment 15 is described
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 4 is obtained is dissolved in 100 milliliters of ethanol, and through centrifugal treating, 3000 revs/min of centrifugal rotational speeds, centrifugation time 25 minutes, obtains supernatant liquor; The supernatant liquor obtaining is through alcohol dilution, and obtaining concentration is the ethanolic soln of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 17 is the ethanolic soln of carbon nano dot of the embodiment of the present invention 15 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 320nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 420nm under exciting, curve 5 is the fluorescence emission spectrogram of 460nm under exciting, and curve 6 is the fluorescence emission spectrogram of 500nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 467nm (excitation wavelength 380nm), maximum fluorescence quantum yield is 18%.
Embodiment 16
In conjunction with Figure 18, embodiment 16 is described
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 5 is obtained is dissolved in 100 ml waters, and through centrifugal treating, 4000 revs/min of centrifugal rotational speeds, centrifugation time 16 minutes, obtains supernatant liquor; The supernatant liquor obtaining dilutes through water, and obtaining concentration is the aqueous solution of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 18 is the aqueous solution of carbon nano dot of the embodiment of the present invention 16 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 320nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 390nm under exciting, curve 5 is the fluorescence emission spectrogram of 400nm under exciting, and curve 6 is the fluorescence emission spectrogram of 460nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 535nm (excitation wavelength 420nm), maximum fluorescence quantum yield is 18%.
Embodiment 17
In conjunction with Figure 19,20 explanation embodiment 17
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 6 is obtained is dissolved in 100 ml waters, and through centrifugal treating, 3000 revs/min of centrifugal rotational speeds, centrifugation time 20 minutes, obtains supernatant liquor; The supernatant liquor obtaining dilutes through water, and obtaining concentration is the aqueous solution of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 19 is the aqueous solution of carbon nano dot of the embodiment of the present invention 17 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 350nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 420nm under exciting, curve 5 is the fluorescence emission spectrogram of 460nm under exciting, curve 6 is the fluorescence emission spectrogram of 480nm under exciting, and curve 7 is the fluorescence emission spectrogram of 500nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 535nm (excitation wavelength 420nm) maximum fluorescence quantum yield is 18%.
Figure 20 is that the carbon nano dot fluorescent ink of the embodiment of the present invention 17 drips on filter paper, and after air drying, fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 320nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 420nm under exciting, curve 5 is the fluorescence emission spectrogram of 460nm under exciting, and curve 6 is the fluorescence emission spectrogram of 480nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 520nm (excitation wavelength 420nm), maximum fluorescence quantum yield is 42%.
Embodiment 18
In conjunction with Figure 21, embodiment 18 is described
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 7 is obtained is dissolved in 100 milliliters of ethanol, and through centrifugal treating, 3000 revs/min of centrifugal rotational speeds, centrifugation time 22 minutes, obtains supernatant liquor; The supernatant liquor obtaining is through alcohol dilution, and obtaining concentration is the ethanolic soln of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 21 is the ethanolic soln of carbon nano dot of the embodiment of the present invention 18 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 340nm under exciting, curve 2 is the fluorescence emission spectrogram of 380nm under exciting, curve 3 is the fluorescence emission spectrogram of 420nm under exciting, curve 4 is the fluorescence emission spectrogram of 460nm under exciting, and curve 5 is the fluorescence emission spectrogram of 500nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 527nm (excitation wavelength 420nm), maximum fluorescence quantum yield is 40%.
Embodiment 19
In conjunction with Figure 22, embodiment 19 is described
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 8 is obtained is dissolved in 100 ml waters, and through centrifugal treating, 3000 revs/min of centrifugal rotational speeds, centrifugation time 25 minutes, obtains supernatant liquor; The supernatant liquor obtaining dilutes through water, and obtaining concentration is the aqueous solution of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 22 is the aqueous solution of carbon nano dot of the embodiment of the present invention 19 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 300nm under exciting, curve 2 is the fluorescence emission spectrogram of 340nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 420nm under exciting, curve 5 is the fluorescence emission spectrogram of 450nm under exciting, and curve 6 is the fluorescence emission spectrogram of 480nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 428nm (excitation wavelength 340nm), maximum fluorescence quantum yield is 10%.
Embodiment 20
In conjunction with Figure 23, embodiment 20 is described
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 9 is obtained is dissolved in 100 ml waters, and through centrifugal treating, 4000 revs/min of centrifugal rotational speeds, centrifugation time 20 minutes, obtains supernatant liquor; The supernatant liquor obtaining dilutes through water, and obtaining concentration is the aqueous solution of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 23 is the aqueous solution of carbon nano dot of the embodiment of the present invention 20 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 300nm under exciting, curve 2 is the fluorescence emission spectrogram of 340nm under exciting, curve 3 is the fluorescence emission spectrogram of 380nm under exciting, curve 4 is the fluorescence emission spectrogram of 420nm under exciting, curve 5 is the fluorescence emission spectrogram of 450nm under exciting, and curve 6 is the fluorescence emission spectrogram of 480nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 420nm (excitation wavelength 340nm), maximum fluorescence quantum yield is 8%.
Embodiment 21
In conjunction with Figure 24, embodiment 21 is described
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 10 is obtained is dissolved in 100 ml waters, and through centrifugal treating, 3000 revs/min of centrifugal rotational speeds, centrifugation time 20 minutes, obtains supernatant liquor; The supernatant liquor obtaining dilutes through water, and obtaining concentration is the aqueous solution of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 24 is the aqueous solution of carbon nano dot of the embodiment of the present invention 21 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 320nm under exciting, curve 2 is the fluorescence emission spectrogram of 360nm under exciting, curve 3 is the fluorescence emission spectrogram of 400nm under exciting, curve 4 is the fluorescence emission spectrogram of 440nm under exciting, and curve 5 is the fluorescence emission spectrogram of 480nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 425nm (excitation wavelength 400nm), maximum fluorescence quantum yield is 6%.
Embodiment 22
In conjunction with Figure 25, embodiment 22 is described
Carbon nano dot of the present invention is in the application of preparing in fluorescent ink:
The carbon nano dot that embodiment 11 is obtained is dissolved in 100 ml waters, and through centrifugal treating, 3000 revs/min of centrifugal rotational speeds, centrifugation time 20 minutes, obtains supernatant liquor; The supernatant liquor obtaining dilutes through water, and obtaining concentration is the aqueous solution of the carbon nano dot of 1 mg/ml, i.e. carbon nano dot fluorescent ink.
Figure 25 is the aqueous solution of carbon nano dot of the embodiment of the present invention 22 fluorescence emission spectrogram under different excitation wavelengths: curve 1 is the fluorescence emission spectrogram of 300nm under exciting, curve 2 is the fluorescence emission spectrogram of 320nm under exciting, curve 3 is the fluorescence emission spectrogram of 340nm under exciting, curve 4 is the fluorescence emission spectrogram of 360nm under exciting, curve 5 is the fluorescence emission spectrogram of 380nm under exciting, curve 6 is the fluorescence emission spectrogram of 420nm under exciting, and curve 7 is the fluorescence emission spectrogram of 460nm under exciting; HyperfluorescenceZeng Yongminggaoyingguang emission peak 390nm (excitation wavelength 340nm), maximum fluorescence quantum yield is 12%.
Claims (10)
1. a carbon nano dot, is characterized in that, this carbon nano dot is to contain many carboxyls or polyhydric organic compound as raw material, or taking amino acid as raw material, is prepared from taking urea as surface passivation agent, and step is as follows:
1. urea with containing many carboxyls or polyhydric organic compound, or amino acid in mass ratio 0.1:1-4:1 be mixed with the aqueous solution;
2. the 1. prepared aqueous solution is reacted and obtained brownish black solid by microwave heating;
3. the brownish black solid obtaining, through heating under vacuum, is removed residual micromolecular compound, obtains carbon nano dot;
Described carbon nano dot surface has amide group and carboxylic group.
2. a kind of carbon nano dot according to claim 1, is characterized in that, described many carboxyls or polyhydric organic compound are citric acid, ethylenediamine tetraacetic acid (EDTA), glycerine, glucose, fructose, sucrose, chitosan or starch.
3. a kind of carbon nano dot according to claim 1, is characterized in that, described amino acid is glycine or L-glutamic acid.
4. a kind of carbon nano dot according to claim 1, is characterized in that, step 1. in, described urea with containing many carboxyls or polyhydric organic compound, or amino acid in mass ratio 0.1:1-4:1 be mixed with saturated aqueous solution.
5. a kind of carbon nano dot according to claim 1, is characterized in that, step 2. in, the described aqueous solution is through 500-900W power microwave heating 3-10 minute.
6. a kind of carbon nano dot according to claim 1, is characterized in that, step 3. in, the vacuum tightness of described heating under vacuum is 0.001-0.1 handkerchief, Heating temperature is 50-70 degree Celsius, heat-up time 1-2 hour.
7. a preparation method for carbon nano dot, is characterized in that, comprises the following steps:
1. urea with containing many carboxyls or polyhydric organic compound, or amino acid in mass ratio 0.1:1-4:1 be mixed with the aqueous solution;
2. the 1. prepared aqueous solution is reacted and obtained brownish black solid by microwave heating;
3. by brownish black solid through heating under vacuum, remove residual micromolecular compound, obtain carbon nano dot.
8. a kind of carbon nano dot of claim 1-6 described in any one is in the application of preparing in fluorescent ink.
9. a kind of carbon nano dot according to claim 8, in the application of preparing in fluorescent ink, is characterized in that, by soluble in water carbon nano dot, through centrifugal, obtains supernatant liquor; The supernatant liquor obtaining, through water or organic solvent diluting, is obtained to carbon nano dot fluorescent ink.
10. a kind of carbon nano dot according to claim 9, in the application of preparing in fluorescent ink, is characterized in that, centrifugal rotational speed is 2000-4000 rev/min, and the time is 15-30 minute.
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