CN105067579A - Preparation and application of single-layer g-C3N4 fluorescence sensor - Google Patents
Preparation and application of single-layer g-C3N4 fluorescence sensor Download PDFInfo
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- CN105067579A CN105067579A CN201510449480.4A CN201510449480A CN105067579A CN 105067579 A CN105067579 A CN 105067579A CN 201510449480 A CN201510449480 A CN 201510449480A CN 105067579 A CN105067579 A CN 105067579A
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- optical sensor
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Abstract
The invention relates to a preparation method and application of a quasi-graphene-based single-layer carbon nitride compound (g-C3N4) fluorescence sensor, which belongs to the technical fields of material science and engineering and modern optical sensing. The preparation method comprises the following steps: with dicyanodiamide as a raw material, preparing block solid g-C3N4 powder by using a temperature-programmed calcining process; and preparing single-layer g-C3N4 colloid in a high aqueous dispersion state from the block solid g-C3N4 by using a liquid exfoliation ultrasonic stripping process so as to obtain the single-layer g-C3N4 fluorescence sensor. The single-layer g-C3N4 colloid has good fluorescence performance and stability and presents obvious Tyndall phenomenon and blue fluorescence characteristics; and the prepared single-layer g-C3N4 fluorescence sensor has selective response performance and is applicable to analysis and detection of trace silver ions in complex samples like organisms, food and environments.
Description
Technical field
The invention belongs to Materials Science and Engineering and contemporary optics field of sensing technologies, relate to individual layer g-C
3n
4the preparation method of fluorescent sensing material and application thereof.This fluorescent optical sensor has good response to silver ion, and the analysis being applicable to Trace Silver ion in the complex samples such as biology, food, environment detects.
Background technology
In recent years, fluorescent optical sensor has catalytic action, electric conductivity, the advantage such as simple to operation, more and more extensive in field application such as biology, environment, chemical industry; Sensor based on fluorescence quenching is one of them important research direction, and sensing new material receives much concern as the cross knot chalaza of material science and analytical chemistry.
Class graphene carbon nitrogen compound (g-C
3n
4) be the high-molecular porous material formed primarily of C and N element, its obtained colloid sheet layer material has wide excitation spectrum, narrow emission spectrum, good fluorescence property and the feature such as excellent biocompatibility and low bio-toxicity, be a kind of than luminescent dye molecule and heavy metal quantum dot more preferably fluorescence probe, have good application prospect in fields such as fluorescence sense, galvanochemistry, catalytic chemistry, adsorptive separation.The people such as Chen adopt high-temperature calcination first to obtain yellow g-C
3n
4powder, and then synthesized the g-C of different proportion
3n
4/ WO
3compound catalyze material, by light degradation methylene blue and magenta, both discoveries have good catalytic activity; The people such as Kumar adopt growth in situ mechanism, and synthesis has the g-C of Magneto separate and Visible Light Induced Photocatalytic rhodamine B
3n
4-Fe
3o
4compound catalyze material.Adopt red fuming nitric acid (RFNA) chemical oxidization method can obtain the g-C of height aqueous dispersion
3n
4nanometer sheet, but the method step is more.In neutral conditions, the people such as Tian adopts ultrasonic assistant liquid exfoliating stripping method to prepare g-C
3n
4ultrathin nanometer sheet, and the Cu in water body environment is detected as fluorescent optical sensor
2+.
Silver is a kind of important industrial materials, it promotes the industrial expansions such as electron trade, plating and machine-building, also result in water body environment pollution simultaneously.Silver ion has toxicity, the bioaccumulation of heavy metal ion, can cause primary cellular defect, brings infringement to people's health.In conjunction with individual layer g-C
3n
4the poriness of fluorescent optical sensor, adsorbability and fluorescent characteristic, carry out individual layer g-C
3n
4the development of fluorescent optical sensor also has important theory significance and practical value for the detection of micro silver ion in Environmental Water.
Summary of the invention
The present invention is directed to required fluorescent optical sensor is detected in the fields such as environment fast demand to micro silver ion, in conjunction with current nanometer sheet g-C both at home and abroad
3n
4the development trend of fluorescent material research, provides a kind of new individual layer g-C
3n
4the preparation method of fluorescent optical sensor.
The present invention is achieved through the following technical solutions:
A kind of individual layer g-C
3n
4the preparation method of fluorescent optical sensor, prepares according to the following steps:
(1) take dicyanodiamine as raw material, adopt temperature programme calcination method to prepare g-C
3n
4pressed powder, for subsequent use;
(2) by g-C obtained for step (1)
3n
4pressed powder is ultrasonic disperse in distilled water, obtained g-C
3n
4suspending liquid;
(3) by g-C obtained for step (2)
3n
4suspending liquid centrifuging, obtained sheet g-C
3n
4dispersion liquid;
(4) by sheet g-C obtained for step (3)
3n
4dispersion liquid is ultrasonic stripping again, the aqueous dispersion of low-speed centrifugal obtained height
Individual layer g-C
3n
4colloid, is described individual layer g-C
3n
4fluorescent optical sensor.
Further, the temperature programme calcination method adopted in described step (1), temperature elevating range be room temperature to 550 DEG C, heating rate 4-6 DEG C/min.
Further, in described step (2), described g-C
3n
4the mass ratio of pressed powder and distilled water is 1:500-1:2000.
Further, in described step (4): g-C
3n
4the time of the ultrasonic stripping of dispersion liquid is 1-2h.
Further, obtained in described step (4) height aqueous dispersion individual layer g-C
3n
4the concentration of colloid is about 0.04mg/mL.
Content of the present invention also comprises the individual layer nanometer sheet g-C prepared according to the method for above-mentioned any
3n
4fluorescent optical sensor.
Further, the present invention also comprises above-mentioned individual layer g-C
3n
4fluorescent optical sensor, analyzes the application detected in Trace Silver ion in Complex water body environment.
Further, described Complex water body environment is environmental water sample.
Further, detecting of silver ion is limited to 52.3nmol/L.
The present invention adopts twice liquid exfoliating legal system to get everything ready the fluorescence porosint of good luminous performance and characterization of adsorption, directly by the g-C of curling bulk
3n
4powder, by ultrasonic stripping, obtains simply, stablizes and the sensor of good fluorescence characteristic.Individual layer g-C of the present invention
3n
4fluorescent optical sensor has selective response to silver ion, can meet the analysis requirement that heavy metal-polluted water Environmental Trace silver ion is residual.
In order to understand better and implement, describe the present invention in detail below in conjunction with accompanying drawing.
Accompanying drawing explanation
Fig. 1 individual layer g-C
3n
4process flow diagram prepared by fluorescent optical sensor.
Fig. 2 is individual layer g-C
3n
4the ultraviolet spectrogram of fluorescent optical sensor and fluorescence spectrum figure, Tyndall effect picture (on) and fluorescent effect picture under uviol lamp (under).
Fig. 3 is individual layer g-C
3n
4the atomic force microscope figure (A) of fluorescent material and thickness of thin layer spectrogram (B).
Fig. 4 individual layer g-C
3n
4the selectivity of fluorescent optical sensor
Fig. 5 individual layer g-C
3n
4to fluorescence response and the range of linearity thereof of variable concentrations silver ion standard solution.
Specific embodiment
Be described below in conjunction with embodiments of the invention, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1 individual layer g-C
3n
4the preparation of fluorescent optical sensor
The present embodiment is individual layer g-C
3n
4the preparation (Fig. 1) of fluorescent optical sensor, concrete steps are as follows:
(1) block g-C
3n
4the preparation of porosint: employing dicyanodiamine is raw material, prepares block g-C by high-temperature calcination
3n
4, synthesis step is specific as follows: take 5g dicyanodiamine pressed powder, holds and put into controlled sequence intensification muffle furnace after grinding with semiclosed porcelain crucible, programmed rate is 4.5 DEG C/min, keep 4h at 520 DEG C, then naturally cool to room temperature, obtain the g-C of yellow curling bulk
3n
4, grind stand-by.
(2) individual layer nanometer sheet g-C
3n
4the preparation of fluorescent sensing material: adopt the synthesis of liquid exfoliating stripping method.Concrete synthesis step is as follows: take the block g-C of 100mg
3n
4, join in the conical flask filling 100mL deionized water, continuous ultrasound 1-2h; By g-C
3n
4suspending liquid is centrifugal 5min under 5000rpm, obtains more stable sheet g-C
3n
4aqueous dispersions; By gained sheet g-C
3n
4aqueous dispersions is ultrasonic 1-2h again, centrifugal, can obtain described individual layer g-C
3n
4colloidal solution.
Obtained individual layer nanometer sheet g-C
3n
4as shown in Figure 3,3 (B) are by any two g-C to sensing material
3n
4the thickness spectrogram that thin slice district obtains.
Embodiment 2: individual layer g-C
3n
4the fluorescence property of fluorescent optical sensor, selectivity
(1) fluorescence property
Fig. 2 gives individual layer g-C
3n
4the ultraviolet spectrogram of fluorescent optical sensor and fluorescence spectrum figure, and Tyndall effect (on) and fluorescent effect under uviol lamp (under).Can find out, this sensor has strong uv absorption at 312nm place; When excitation wavelength is 365nm, the position of its fluorescence emission peak at 435nm, and shows narrow emission peak.After adopting twice ultrasonic stripping of liquid exfoliating, individual layer g-C
3n
4there is strong blue light characteristic under uviol lamp; Under a branch of Infrared irradiation, appear as obvious Tyndall phenomenon, individual layer g-C is described
3n
4colloid can stable existence in water.
(2) selectivity
Fig. 4 gives individual layer g-C
3n
4fluorescent optical sensor is to Fe
3+, Ba
2+, Be
2+, Hg
2+, K
+, Mn
2+, Zn
2+, Pb
2+, Cr
3+, Mg
2+, Ni
2+, Co
2+, Ca
2+, Cd
2+and Al
3+isoionic fluorescence response, result shows that fluorescent optical sensor has silver ion and optionally responds; Compared with silver ion, the impact of other ion is very little, can ignore.
embodiment 3:individual layer g-C
3n
4the application of silver ion in fluorescent optical sensor testing environment water
(1) foundation of analytical approach
Prepare the silver ion standard solution that a series of concentration is 0.165 to 33.0 μm of ol/L, respond drawing standard curve by fluorescence spectrum and calculate the range of linearity, related coefficient and method detection limit.Result shows, Ag
+linear relationship good (Fig. 5) when the concentration of ion is 0.165-1.65 μm of ol/L, linear equation is Δ F=9.836+1.443C, and related coefficient 0.993, detects and be limited to 52.3nmol/L.
(2) actual sample analysis
Institute's construction method is applied in Environmental Water the analysis of silver ion is detected.And 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 rainwater, tap water, mineral water and Pearl River water, fully for subsequent use after mixing.
The actual water sample and the silver ion mixed liquor that pipette 10,20 and 50 μ L respectively join 1mL individual layer g-C
3n
4in colloidal solution, be settled to 2mL with water, shake up in rear 1min and detect, measure its fluorescence intensity.According to formula:
Result shows, the recovery 80.8%-115.8% of silver ion, RSD is less than 0.8%.
The above, the fluorescence porosint that the present invention adopts grinding to calcine and repeatedly the preparation of liquid exfoliating lift-off technology has the adsorbability that strong luminescent properties is become reconciled, directly by the g-C of curling bulk
3n
4powder, by twice ultrasonic stripping, obtains the fluorescent optical sensor of simple, stable and good fluorescent characteristic.Individual layer g-C of the present invention
3n
4fluorescent optical sensor, can have silver ion and optionally respond, and meets the analysis requirement that heavy metal pollution of water body Environmental Trace silver ion is residual.
It is to be understood that, below be only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be do not depart from technical solution of the present invention content, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still, belong in the scope of technical solution of the present invention.
Claims (9)
1. an individual layer g-C
3n
4the preparation method of fluorescent optical sensor, is characterized in that, prepares according to the following steps:
(1) take dicyanodiamine as raw material, adopt temperature programme calcination method to prepare g-C
3n
4pressed powder, for subsequent use;
(2) by g-C obtained for step (1)
3n
4pressed powder is ultrasonic disperse in distilled water, obtained g-C
3n
4suspending liquid;
(3) by g-C obtained for step (2)
3n
4suspending liquid centrifuging, obtained sheet g-C
3n
4dispersion liquid;
(4) by sheet g-C obtained for step (3)
3n
4dispersion liquid is ultrasonic stripping again, and low-speed centrifugal obtains the individual layer g-C of height aqueous dispersion
3n
4colloid, is described individual layer g-C
3n
4fluorescent optical sensor.
2. individual layer g-C as claimed in claim 1
3n
4the preparation method of fluorescent optical sensor, is characterized in that: the temperature programme calcination method adopted in described step (1), temperature elevating range be room temperature to 550 DEG C, heating rate 4-6 DEG C/min.
3. individual layer g-C as claimed in claim 1
3n
4the preparation method of fluorescent optical sensor, is characterized in that: in described step (2), described g-C
3n
4the mass ratio of pressed powder and distilled water is 1:500-1:2000.
4. individual layer g-C as claimed in claim 1
3n
4the preparation method of fluorescent optical sensor, is characterized in that: in described step (4): g-C
3n
4the time of the ultrasonic stripping of dispersion liquid is 1-2h.
5. individual layer g-C as claimed in claim 1
3n
4the preparation method of fluorescent optical sensor, is characterized in that: height aqueous dispersion individual layer g-C obtained in described step (4)
3n
4colloid concentration is about 0.04mg/mL.
6. according to the individual layer nanometer sheet g-C that the method for any one of claim 1-5 prepares
3n
4fluorescent optical sensor.
7. individual layer g-C according to claim 6
3n
4fluorescent optical sensor, analyzes to detect in Trace Silver ion and applies in Complex water body environment.
8. apply as claimed in claim 7, it is characterized in that: described Complex water body environment is environmental water sample.
9. apply as claimed in claim 7, it is characterized in that: detecting of silver ion is limited to 52.3nmol/L.
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| CN201510449480.4A CN105067579B (en) | 2015-07-28 | 2015-07-28 | A kind of single layer g-C3N4The preparation and its application of fluorescent optical sensor |
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Cited By (5)
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| CN105692573A (en) * | 2016-03-29 | 2016-06-22 | 中国人民解放军国防科学技术大学 | Preparation method of nano-structure carbon nitride |
| CN106824190A (en) * | 2017-03-03 | 2017-06-13 | 中国科学技术大学先进技术研究院 | A kind of WO3‑xNanocatalyst and its preparation, application |
| CN107790168A (en) * | 2017-10-31 | 2018-03-13 | 北京化工大学 | A kind of preparation method of hydrogenation catalyst and fluorescence saturated rubber with fluorescence |
| CN110455757A (en) * | 2019-08-05 | 2019-11-15 | 广州大学 | A kind of ratio fluorescent detection method of para-nitrotoluene |
| CN113046075A (en) * | 2021-03-26 | 2021-06-29 | 东南大学 | Optical metal-based modified gel and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105692573A (en) * | 2016-03-29 | 2016-06-22 | 中国人民解放军国防科学技术大学 | Preparation method of nano-structure carbon nitride |
| CN106824190A (en) * | 2017-03-03 | 2017-06-13 | 中国科学技术大学先进技术研究院 | A kind of WO3‑xNanocatalyst and its preparation, application |
| CN106824190B (en) * | 2017-03-03 | 2023-12-29 | 中国科学技术大学先进技术研究院 | WO (WO) 3-x Nanometer catalyst and its preparation and application |
| CN107790168A (en) * | 2017-10-31 | 2018-03-13 | 北京化工大学 | A kind of preparation method of hydrogenation catalyst and fluorescence saturated rubber with fluorescence |
| CN107790168B (en) * | 2017-10-31 | 2020-04-10 | 北京化工大学 | Hydrogenation catalyst with fluorescence and preparation method of fluorescence saturated rubber |
| CN110455757A (en) * | 2019-08-05 | 2019-11-15 | 广州大学 | A kind of ratio fluorescent detection method of para-nitrotoluene |
| CN110455757B (en) * | 2019-08-05 | 2022-02-22 | 广州大学 | Fluorescence ratio detection method for p-nitrotoluene |
| CN113046075A (en) * | 2021-03-26 | 2021-06-29 | 东南大学 | Optical metal-based modified gel and preparation method and application thereof |
| CN113046075B (en) * | 2021-03-26 | 2022-03-15 | 东南大学 | Optical metal-based modified gel and preparation method and application thereof |
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