CN105067579B - A kind of single layer g-C3N4The preparation and its application of fluorescent optical sensor - Google Patents

A kind of single layer g-C3N4The preparation and its application of fluorescent optical sensor Download PDF

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CN105067579B
CN105067579B CN201510449480.4A CN201510449480A CN105067579B CN 105067579 B CN105067579 B CN 105067579B CN 201510449480 A CN201510449480 A CN 201510449480A CN 105067579 B CN105067579 B CN 105067579B
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single layer
optical sensor
fluorescent optical
silver ion
water
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CN105067579A (en
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曹玉娟
王颂
吴威
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South China Normal University
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South China Normal University
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Abstract

The invention belongs to Materials Science and Engineerings and contemporary optics field of sensing technologies, are related to a kind of single layer carboritride (g C based on class graphene3N4) fluorescent optical sensor preparation method and applications.Steps are as follows:Using dicyanodiamine as raw material, blocks of solid g C are prepared using temperature programming calcination method3N4Powder;Then use liquid exfoliating ultrasound stripping method by g C3N4Blocks of solid is prepared as height single layer g C water-dispersed3N4Colloid, the as described single layer g C3N4Fluorescent optical sensor.The single layer g C of the present invention3N4Colloid has good fluorescence property and stability, shows apparent Tyndall phenomenon and blue-fluorescence characteristic, which has selective response to silver ion, the analysis detection of trace silver ion suitable for the complex samples such as biology, food, environment.

Description

A kind of single layer g-C3N4The preparation and its application of fluorescent optical sensor
Technical field
The invention belongs to Materials Science and Engineerings and contemporary optics field of sensing technologies, are related to single layer g-C3N4Fluorescence passes Feel the preparation method and applications of material.The fluorescent optical sensor to silver ion have good response, be suitable for biology, food, The analysis detection of trace silver ion in the complex samples such as environment.
Background technology
In recent years, fluorescent optical sensor has many advantages, such as catalytic action, electric conductivity, simple to operation, in biology, environment, change The fields such as work are using more and more extensive;Sensor based on fluorescence quenching is one of important research direction, and is sensed New material is concerned as the intersection binding site of material science and analytical chemistry.
Class graphene carbon nitrogen compound (g-C3N4) it is the high-molecular porous material being mainly made of C and N element, it is made Colloid sheet layer material have wide excitation spectrum, narrow emission spectrum, good fluorescence property and excellent biocompatibility And the features such as low bio-toxicity, it is a kind of than luminescent dye molecule and heavy metal quantum dot more preferably fluorescence probe, There is good application prospect in the fields such as fluorescence sense, electrochemistry, catalytic chemistry, adsorbing separation.Chen et al. uses high-temperature calcination Method first obtains the g-C of yellow3N4Powder, and then synthesized the g-C of different proportion3N4/WO3Composite catalyzing material, passes through light degradation Methylene blue and magenta find that the two has good catalytic activity;Kumar et al. uses growth in situ mechanism, synthesis to have The g-C of Magneto separate and Visible Light Induced Photocatalytic rhodamine B3N4-Fe3O4Composite catalyzing material.It can be obtained using concentrated nitric acid chemical oxidization method G-C highly water-dispersed3N4Nanometer sheet, but this method step is more.In neutral conditions, Tian et al. is assisted using ultrasonic wave Liquid exfoliating stripping method is prepared for g-C3N4Ultrathin nanometer piece, and the Cu in water body environment is detected as fluorescent optical sensor2+
Silver is a kind of important industrial materials, it promotes the industrial expansions such as electronics industry, plating and machine-building, together When also result in water body environment pollution.Silver ion has toxicity, the bioaccumulation of heavy metal ion, cell can be caused to damage Evil, damage is brought to people's body.In conjunction with single layer g-C3N4Porosity, adsorptivity and the fluorescent characteristic of fluorescent optical sensor are carried out single Layer g-C3N4The development of fluorescent optical sensor simultaneously has important theory significance and reality for detecting for micro silver ion in ambient water With value.
Invention content
The present invention quickly detects micro silver ion for fields such as environment the demand of required fluorescent optical sensor, in conjunction with current Domestic and international nanometer sheet g-C3N4The development trend of fluorescent material research, provides a kind of new single layer g-C3N4The system of fluorescent optical sensor Preparation Method.
The invention is realized by the following technical scheme:
A kind of single layer g-C3N4The preparation method of fluorescent optical sensor, prepares according to the following steps:
(1) using dicyanodiamine as raw material, g-C is prepared using temperature programming calcination method3N4Solid powder, it is spare;
(2) by g-C made from step (1)3N4G-C is made in solid powder ultrasonic disperse in distilled water3N4Suspension;
(3) by g-C made from step (2)3N4Suspension centrifuges, and sheet g-C is made3N4Dispersion liquid;
(4) by sheet g-C made from step (3)3N4Dispersion liquid ultrasound stripping again, it is water-dispersed that height is made in low-speed centrifugal
Single layer g-C3N4Colloid, the as described single layer g-C3N4Fluorescent optical sensor.
Further, the temperature programming calcination method used in the step (1), temperature elevating range are room temperature to 550 DEG C, heating 4-6 DEG C of rate/min.
Further, in the step (2), the g-C3N4The mass ratio of solid powder and distilled water is 1:500-1: 2000。
Further, in the step (4):g-C3N4The time of dispersion liquid ultrasound stripping is 1-2h.
Further, height single layer g-C water-dispersed obtained in the step (4)3N4The concentration of colloid is about 0.04mg/ mL。
Present disclosure further includes the individual layer nanometer sheet g-C prepared according to above-mentioned any one method3N4Fluorescence Sensor.
Further, the invention also includes above-mentioned single layer g-C3N4Fluorescent optical sensor analyzes detection in Complex water body environment Application in trace silver ion.
Further, the Complex water body environment is environmental water sample.
Further, the detection of silver ion is limited to 52.3nmol/L.
The present invention prepares the porous material of fluorescence with good luminous performance and characterization of adsorption using the method for liquid exfoliating twice Material, will directly crimp block-like g-C3N4Powder is removed by ultrasound, obtains simple, stable and good fluorescence characteristic sensor. The single layer g-C of the present invention3N4Fluorescent optical sensor has selective response to silver ion, can meet in heavy metal-polluted water environment The analysis requirement of Trace Silver ion residues.
In order to better understand and implement, the invention will now be described in detail with reference to the accompanying drawings.
Description of the drawings
Fig. 1 single layers g-C3N4Flow chart prepared by fluorescent optical sensor.
Fig. 2 is single layer g-C3N4The ultraviolet spectrogram and fluorescence spectra of fluorescent optical sensor, Tyndall effect picture (on) and In the UV lamp fluorescent effect picture (under).
Fig. 3 is single layer g-C3N4The atomic force microscopy diagram (A) and thickness of thin layer spectrogram (B) of fluorescent material.
Fig. 4 single layers g-C3N4The selectivity of fluorescent optical sensor
Fig. 5 single layers g-C3N4To the fluorescence response and its range of linearity of various concentration silver ion standard solution.
Specific embodiment
It is illustrated below in conjunction with the embodiment of the present invention, it should be understood that preferred embodiment described herein is only used for The description and interpretation present invention, is not intended to limit the present invention.
1 single layer g-C of embodiment3N4The preparation of fluorescent optical sensor
The present embodiment is single layer g-C3N4The preparation (Fig. 1) of fluorescent optical sensor, is as follows:
(1) bulk g-C3N4The preparation of porous material:It uses dicyanodiamine for raw material, bulk g- is prepared by high-temperature calcination C3N4, synthesis step is specific as follows:5g dicyanodiamine solid powders are weighed, being held and be put into semiclosed porcelain crucible after grinding can It controls in temperature programming Muffle furnace, programmed rate is 4.5 DEG C/min, 4h is kept at 520 DEG C, then cooled to room temperature, It obtains yellow and crimps block-like g-C3N4, grinding is for use.
(2) individual layer nanometer sheet g-C3N4The preparation of fluorescent sensing material:It is synthesized using liquid exfoliating stripping method.Specifically Synthesis step is as follows:Weigh 100mg bulks g-C3N4, it is added in the conical flask for filling 100mL deionized waters, continuous ultrasound 1- 2h;By g-C3N4Suspension centrifuges 5min at 5000rpm, the sheet g-C relatively stablized3N4Aqueous dispersions;By gained sheet g-C3N4Aqueous dispersions ultrasound 1-2h again, centrifugation, you can obtain the single layer g-C3N4Colloidal solution.
Individual layer nanometer sheet g-C is made3N4Sensing material is as shown in figure 3,3 (B) are to pass through arbitrary two g-C3N4Thin slice area obtains Thickness spectrogram.
Embodiment 2:Single layer g-C3N4The fluorescence property of fluorescent optical sensor, selectivity
(1) fluorescence property
Fig. 2 gives single layer g-C3N4The ultraviolet spectrogram and fluorescence spectra and Tyndall effect of fluorescent optical sensor (on) and in the UV lamp fluorescent effect (under).As can be seen that the sensor has strong UV absorption at 312nm;When sharp When hair wavelength is 365nm, the position of fluorescence emission peak shows narrow emission peak in 435nm.It is chamfered using liquid twice After the stripping of matter ultrasound, single layer g-C3N4There is strong blue light characteristic in the UV lamp;Under a branch of Infrared irradiation, appear as bright Aobvious Tyndall phenomenon illustrates single layer g-C3N4Colloid can be stabilized in water.
(2) selectivity
Fig. 4 gives single layer g-C3N4Fluorescent optical sensor is to Fe3+、Ba2+、Be2+、Hg2+、K+、Mn2+、Zn2+、Pb2+、 Cr3+、 Mg2+、Ni2+、Co2+、Ca2+、Cd2+And Al3+The fluorescence response of plasma, the results showed that fluorescent optical sensor has selection to silver ion The response of property;Compared with silver ion, the influence very little of other ions can be ignored.
Embodiment 3:Single layer g-C3N4Fluorescent optical sensor detects the application of silver ion in ambient water
(1) foundation of analysis method
A series of silver ion standard solution for preparing a concentration of 0.165 to 33.0 μm of ol/L is painted by fluorescence spectrum response Standard curve processed simultaneously calculates the range of linearity, related coefficient and method detection limit.The result shows that Ag+A concentration of 0.165- of ion Linear relationship is good (Fig. 5) when 1.65 μm of ol/L, and linear equation is Δ F=9.836+1.443C, related coefficient 0.993, detection It is limited to 52.3nmol/L.
(2) actual sample is analyzed
Institute's construction method is applied to the analysis in ambient water to silver ion to detect.And in rainwater, tap water, mineral water and pearl The silver ion that concentration is respectively 0.33,0.66 and 1.65 μm of ol/L is added in the water samples such as river, is mixed well rear spare.
The actual water sample of 10,20 and 50 μ L is pipetted respectively and silver ion mixed liquor is added to 1mL single layers g-C3N4Colloidal solution In, it is settled to 2mL with water, detection in rear 1min is shaken up, measures its fluorescence intensity.According to formula:
The result shows that the rate of recovery 80.8%-115.8%, RSD of silver ion are less than 0.8%.
The above, the present invention is prepared using grinding calcining and multiple liquid exfoliating lift-off technology has strong photism The fluorescence porous material for the adsorptivity that can be become reconciled, will directly crimp block-like g-C3N4Powder is removed by ultrasound twice, obtains letter The fluorescent optical sensor of single, stable and good fluorescent characteristic.The single layer g-C of the present invention3N4Fluorescent optical sensor, can be to silver ion Selective response meets the remaining analysis requirement of heavy metal pollution of water body Environmental Trace silver ion.
It is to be understood that the foregoing is merely the preferred embodiments of the present invention, any form not is made to the present invention On limitation, although the present invention has been disclosed as a preferred embodiment, however, it is not intended to limit the invention, and any to be familiar with sheet special The technical staff of industry, without departing from the scope of the present invention, when the technology contents using the disclosure above make it is a little The equivalent embodiment of equivalent variations is changed or is modified to, as long as being without departing from technical solution of the present invention content, according to the present invention Technical spirit still falls within the technology of the present invention side to any simple modification, equivalent variations and modification made by above example In the range of case.

Claims (5)

1. a kind of single layer g-C3N4The preparation method of fluorescent optical sensor, which is characterized in that prepare according to the following steps:
(1) using dicyanodiamine as raw material, g-C is prepared using temperature programming calcination method3N4Solid powder, temperature elevating range arrive for room temperature 550 DEG C, heating rate is 4~6 DEG C/min, spare;
(2) by g-C made from step (1)3N4G-C is made in solid powder 1~2h of ultrasonic disperse in distilled water3N4Suspension;Institute State g-C3N4The mass ratio of solid powder and distilled water is 1:500-1:2000;
(3) by g-C made from step (2)3N4Suspension centrifuges, and sheet g-C is made3N4Dispersion liquid;
(4) by sheet g-C made from step (3)3N41~2h of ultrasound stripping, low-speed centrifugal are made a concentration of to dispersion liquid again The height of 0.04mg/mL single layer g-C water-dispersed3N4Colloid, the as described single layer g-C3N4Fluorescent optical sensor.
2. the single layer g-C prepared according to method of claim 13N4Fluorescent optical sensor.
3. the single layer g-C described in claim 23N4Fluorescent optical sensor, in Complex water body environment in analysis detection trace silver ion Using.
4. application as claimed in claim 3, it is characterised in that:The Complex water body environment is environmental water sample.
5. application as claimed in claim 3, it is characterised in that:The detection of silver ion is limited to 52.3nmol/L.
CN201510449480.4A 2015-07-28 2015-07-28 A kind of single layer g-C3N4The preparation and its application of fluorescent optical sensor Expired - Fee Related CN105067579B (en)

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