CN105004773A - Method for preparation of chitosan-graphene quantum dot nanocomposite and for electrochemical detection of heavy metal ions by using chitosan-graphene quantum dot nanocomposite-modified electrode - Google Patents
Method for preparation of chitosan-graphene quantum dot nanocomposite and for electrochemical detection of heavy metal ions by using chitosan-graphene quantum dot nanocomposite-modified electrode Download PDFInfo
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Abstract
The invention relates to a method for preparation of a chitosan-graphene quantum dot nanocomposite and for simultaneous electrochemical detection of Zn<2+>, Cd<2+> and Pb<2+> through combined usage of a chitosan-graphene quantum dot nanocomposite-modified electrode and a bismuth membrane. The method comprises the following steps: preparation of chitosan-graphene quantum dots; preparation of the chitosan-graphene quantum dot nanocomposite; preparation of the chitosan-graphene quantum dot nanocomposite-modified electrode; and simultaneous electrochemical detection of Zn<2+>, Cd<2+> and Pb<2+> through combined usage of the chitosan-graphene quantum dot nanocomposite-modified electrode and the bismuth membrane. The invention has the following advantages: the preparation method for the chitosan-graphene quantum dot nanocomposite is simple and easily practicable; preparation process is environment-friendly and pollution-free; and the chitosan-graphene quantum dot nanocomposite/bismuth membrane modified electrode can realize simultaneous and high-sensitivity detection of Zn<2+>, Cd<2+> and Pb<2+>.
Description
Technical field
The present invention relates to the preparation of a kind of shitosan-graphene quantum dot nano composite material and its modified electrode to be combined with bismuth film and to detect Zn by electrochemical process simultaneously
2+, Cd
2+and Pb
2+, belong to nano material preparation and Electrochemical Detection research field.
Technical background
In recent years, people more and more pay close attention to sustainable development and the natural polymer of environment-friendly type.Shitosan (CS), kation (1-4)-2-amino-2-deoxidation-callose, is generally obtained by chitin deacetylase effect, is one of natural polymer that the earth enriches the most.Have good biocompatibility, biodegradable, the many merits such as polyfunctional group, shitosan causes more concern in packaging for foodstuff, water treatment, UF membrane, organizational project and medicament slow release field.However, shitosan limits it because its physical strength is low and applies widely.Nanometer composite technology, by utilizing as materials such as carbon nano-tube, graphene oxide, clays, can effectively address this problem.When Nano filling has best molecular scale in shitosan inside, and dispersedly it all can be made to reach maximum machinery strengthen.
Graphene quantum dot (GQDs) receives as a kind of novel zero dimension carbon nanomaterial and pays close attention to widely.Because it has many merits, as water-soluble, luminescent properties, resistance to photobleaching, good biocompatibility, the nontoxic and surperficial easy functionalization of excellence, be applied to the field such as photovoltaic device, cell imaging.Compare the material with carbon element such as carbon nano-tube and Graphene, GQDs has less size and better dispersiveness, and GQDs is scattered in polymeric matrix as Nano filling, significantly can improve the mechanical property of material.
In polymeric matrix, dispersion and interfacial adhesion good are between the two vital factors to Nano filling equably.GQDs is because its rich surface is containing-COOH and-OH hydrophilic radical, and when it is water-soluble, surface is height negative charge, is obviously because the result of carboxyl ionization.On the other hand, CS, as a kind of hydrophilic polymer, has-NH in each unit
2with-OH, CS is protonated in acid medium, and being conducive to its polymer chain as a kind of polycationic material with GQDs, electrostatic interaction can occur, and combines closely.By the mode of self assembly using GQDs as Nano filling dispersion with polymeric matrix, this reaction is simply effective, and the good and environmental friendliness of reaction gained shitosan/graphene quantum dot (CS-GQDs) nano composite material pattern.This nano composite material has larger specific surface area and surface containing comparatively polyfunctional group, be easy to and metallic ion coordination, detects three heavy metal species ion Zn delicately while that its modified electrode being combined with bismuth film and realizing by we
2+, Cd
2+and Pb
2+.
Summary of the invention
The object of the invention is to be to provide the preparation of a kind of shitosan-graphene quantum dot nano composite material and its modified electrode and bismuth film connected applications to detect Zn in electrochemical process simultaneously
2+, Cd
2+and Pb
2+.Shitosan-graphene quantum dot nano composite material is modified after glass-carbon electrode, can realize efficiently simultaneously in conjunction with bismuth film and detect three heavy metal species ion Zn delicately
2+, Cd
2+and Pb
2+.
The preparation of a kind of shitosan-graphene quantum dot nano composite material of the present invention and its modified electrode and bismuth film connected applications detect Zn in electrochemical process simultaneously
2+, Cd
2+and Pb
2+, comprise the following steps:
A, prepare graphene quantum dot: take after citric acid solid grinds to form white powder and add in crucible, carry out adding thermal response with program control cabinet-type electric furnace.After reaction terminates, take out solid sample, add appropriate ultrapure water, ultrasonic dissolution.After product fully dissolves, suction filtration obtains yellow transparent solution, keeps in Dark Place under normal temperature.
B, prepare shitosan-graphene quantum dot nano composite material: configure certain density chitosan solution, Chitosan powder is dissolved in the acetum of 0.1M, after stirring and dissolving, dropwise add graphene quantum dot solution, Keep agitation in course of reaction, drip sodium hydroxide solution to certain pH value, separating out yellow solid precipitate thing is shitosan-graphene quantum dot nano composite material, freeze drying 24 hours.
C, prepare shitosan-graphene quantum dot nano composite material modified electrode: by graphene quantum dot-Chitosan Composites ultrasonic disperse in ultrapure water, pipette a certain amount of dispersant liquid drop with liquid-transfering gun and be applied to glassy carbon electrode surface, at room temperature dry 1h.
D, electrochemical process detect Zn simultaneously
2+, Cd
2+and Pb
2+: this experiment use square wave stripping voltammetry (SWSV) measures the Zn in water
2+, Cd
2+and Pb
2+.Experiment adopts three-electrode system, and wherein working electrode is shitosan-graphene quantum dot compound substance modified glassy carbon electrode (diameter 3mm), and platinized platinum is auxiliary electrode, the three-electrode system that saturated calomel electrode (SCE) is contrast electrode.Shitosan-graphene quantum dot nano composite material modified electrode is placed in NaAc-HAc buffer solution (containing bismuth ion/Bi
3+), and in this buffer solution, add certain concentration Zn to be measured
2+, Cd
2+and Pb
2+, stir and enrichment under negative potential, after static, use SWSV to Zn
2+, Cd
2+and Pb
2+stripping peak current carry out record.
The preparation of a kind of shitosan-graphene quantum dot nano composite material of the present invention and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously
2+, Cd
2+and Pb
2+, further technical scheme can also be in described step a, and citric acid quality is 0.2 ~ 20.0g, and temperature of reaction is 100 ~ 300 DEG C, and the reaction time is 0.1 ~ 2h, and during dissolved solid product, ultrapure water used is 2 ~ 20mL.
The preparation of a kind of shitosan-graphene quantum dot nano composite material of the present invention and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously
2+, Cd
2+and Pb
2+, further technical scheme can also be in described step b, and chitosan solution concentration is 0.2 ~ 20mg/mL, and graphene quantum dot solution concentration is 0.2 ~ 20mg/mL, and dripping sodium hydroxide solution is 2 ~ 8 to pH.
The preparation of a kind of shitosan-graphene quantum dot nano composite material of the present invention and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously
2+, Cd
2+and Pb
2+, further technical scheme can also be in described step c, and the volume that liquid-transfering gun pipettes dispersion liquid is 1 ~ 10 μ L, and concentration is 0.2 ~ 20mg/mL.
The preparation of a kind of shitosan-graphene quantum dot nano composite material of the present invention and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously
2+, Cd
2+and Pb
2+, further technical scheme can also be in described steps d, and NaAc-HAc volume of buffer solution is 2 ~ 50mL, and concentration is 0.01 ~ 10mol/L; Bi in solution
3+concentration is 100 ~ 10000 μ g/L, Zn
2+, Cd
2+and Pb
2+concentration is 50 ~ 500 μ g/L; Accumulating potential is-2.0 ~-1.0V, and enrichment time is 300 ~ 900s, and rest time is 1 ~ 30s.
Beneficial effect of the present invention is: the preparation method of shitosan-graphene quantum dot nano composite material is simple and easy to do, and preparation process is environment friendly and pollution-free, and shitosan-graphene quantum dot/bismuth film modified electrode is for Zn
2+, Cd
2+and Pb
2+can realize simultaneously and highly sensitive detection.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is shitosan in embodiment one-graphene quantum dot nano composite material scanning electron microscope (SEM) photograph;
Fig. 2 is shitosan in embodiment one-graphene quantum dot nano composite material transmission electron microscope picture;
In Fig. 3 embodiment two, shitosan-graphene quantum dot/bismuth film modified electrode is to Zn
2+, Cd
2+and Pb
2+implement to detect simultaneously;
Fig. 4 be graphene quantum dot in comparative example one/bismuth film modified electrode (curve a), shitosan in comparative example two/bismuth film modified electrode (curve b), and in comparative example three shitosan-graphene quantum dot (without bismuth film) (curve c) modified electrode to Zn
2+, Cd
2+and Pb
2+implement to detect simultaneously;
Embodiment
The present invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment one:
Prepare shitosan-graphene quantum dot nano composite material and comprise following step:
(1) taking after 2.0g citric acid grinds to form white powder adds in 10mL crucible, adds thermal response 0.5h with program control cabinet-type electric furnace under 200 DEG C of conditions.After reaction terminates, take out solid sample, add 10mL ultrapure water, ultrasonic dissolution.After product fully dissolves, suction filtration obtains yellow transparent solution, keeps in Dark Place under normal temperature.
(2) configuration concentration is the chitosan solution of 2mg/mL, Chitosan powder is dissolved in the acetum of 0.1M, after stirring and dissolving, dropwise add 2mg/mL graphene quantum dot solution, Keep agitation in course of reaction, dripping sodium hydroxide solution is 4.5 to pH, and separating out yellow solid precipitate thing is shitosan-graphene quantum dot nano composite material, freeze drying 24 hours.Have comparatively Large ratio surface area by electrostatic self-assembled legal system for gained shitosan-graphene quantum dot nano composite material, the structure of its bulk multi-hole can be found out from accompanying drawing 1.In addition, can be found out by the transmission electron microscope picture of accompanying drawing 2, graphene quantum dot is dispersed in chitosan basal body uniformly as nano-composite material.This nano composite material has the spongy pattern of good class, and applicable is applied to electrode surface and detects metallic ion.
Embodiment two:
Shitosan-graphene quantum dot/bismuth film modified electrode is to Zn
2+, Cd
2+and Pb
2+implement to detect to comprise following step simultaneously:
(1) by graphene quantum dot-Chitosan Composites ultrasonic disperse in ultrapure water, the dispersant liquid drop pipetting 5 μ L (2mg/mL) with liquid-transfering gun is applied to glassy carbon electrode surface, at room temperature dry 1h.
(2) this experiment use square wave stripping voltammetry (SWSV) measures the Zn in water
2+, Cd
2+and Pb
2+.Experiment adopts three-electrode system, and wherein working electrode is shitosan-graphene quantum dot compound substance modified glassy carbon electrode (diameter 3mm), and platinized platinum is auxiliary electrode, the three-electrode system that saturated calomel electrode (SCE) is contrast electrode.Shitosan-graphene quantum dot nano composite material modified electrode is placed in 20mL 0.1mol/L NaAc-HAc buffer solution (pH=5.5) (containing the Bi of 1000 μ g/L
3+), and in this buffer solution, add certain concentration Zn to be measured
2+, Cd
2+and Pb
2+(300 μ g/L), stirs and enrichment 600s under-1.5V current potential, after static 15s, uses SWSV (-1.4 ~-0.3V) to Zn
2+, Cd
2+and Pb
2+stripping peak current carry out record.Wherein, three kinds of ion detection concentration ranges are 50 ~ 450 μ g/L, and zinc ion equation of linear regression is I=0.01425C+0.03055, detect and are limited to 8.84 μ g/L; Cadmium ion equation of linear regression is I=0.05574C+0.27507, and detection is limited to 1.99 μ g/L and lead ion equation of linear regression is I=0.0465C+0.48815, detects and is limited to 3.10 μ g/L (S/N=3).It is 4.2%, 3.7% and 4.8% respectively that five experiment relative standard deviations are respectively zinc ion, cadmium ion and lead ion.
Comparative example one:
Graphene quantum dot/bismuth film modified electrode is to Zn
2+, Cd
2+and Pb
2+implement to detect to comprise following step simultaneously:
(1) taking after 2.0g citric acid grinds to form white powder adds in 10mL crucible, adds thermal response 0.5h with program control cabinet-type electric furnace under 200 DEG C of conditions.After reaction terminates, take out solid sample, add 10mL ultrapure water, ultrasonic dissolution.After product fully dissolves, suction filtration obtains yellow transparent solution, keeps in Dark Place under normal temperature.Dispersant liquid drop graphene quantum dot liquid-transfering gun being pipetted 5 μ L (2mg/mL) is applied to glassy carbon electrode surface, at room temperature dry 1h.
(2) this experiment use square wave stripping voltammetry (SWSV) measures the Zn in water
2+, Cd
2+and Pb
2+.Experiment adopts three-electrode system, and wherein working electrode is modified by graphene quantum dot glass-carbon electrode (diameter 3mm), and platinized platinum is auxiliary electrode, the three-electrode system that saturated calomel electrode (SCE) is contrast electrode.Modified by graphene quantum dot electrode is placed in 20mL 0.1mol/L NaAc-HAc buffer solution (pH=5.5) (containing the Bi of 1000 μ g/L
3+), and in this buffer solution, add certain concentration Zn to be measured
2+, Cd
2+and Pb
2+(300 μ g/L), stirs and enrichment 600s under-1.5V current potential, after static 15s, uses SWSV (-1.4 ~-0.3V) to Zn
2+, Cd
2+and Pb
2+stripping peak current carry out record.Experimental result shows (Fig. 4), and (curve a) is starkly lower than shitosan-graphene quantum dot/bismuth film modified electrode (curve d) to the Detection results of metallic ion to single modified by graphene quantum dot electrode.
Comparative example two:
Shitosan/bismuth film modified electrode is to Zn
2+, Cd
2+and Pb
2+implement to detect to comprise following step simultaneously:
(1) configuration concentration is the chitosan solution of 2mg/mL, Chitosan powder is dissolved in the acetum of 0.1M, after stirring and dissolving, drips sodium hydroxide solution and separates out to solid sediment, freeze drying 24 hours.By shitosan ultrasonic disperse in ultrapure water, the dispersant liquid drop pipetting 5 μ L (2mg/mL) with liquid-transfering gun is applied to glassy carbon electrode surface, at room temperature dry 1h.
(2) this experiment use square wave stripping voltammetry (SWSV) measures the Zn in water
2+, Cd
2+and Pb
2+.Experiment adopts three-electrode system, and wherein working electrode is shitosan electrode (diameter 3mm), and platinized platinum is auxiliary electrode, the three-electrode system that saturated calomel electrode (SCE) is contrast electrode.Dispersant liquid drop chitosan dispersion liquid-transfering gun being pipetted 5 μ L (2mg/mL) is applied to glassy carbon electrode surface, at room temperature dry 1h.Chitosan-modified electrode is placed in 20mL 0.1mol/L NaAc-HAc buffer solution (pH=5.5) (containing the Bi of 1000 μ g/L
3+), and in this buffer solution, add certain concentration Zn to be measured
2+, Cd
2+and Pb
2+(300 μ g/L), stirs and enrichment 600s under-1.5V current potential, after static 15s, uses SWSV (-1.4 ~-0.3V) to Zn
2+, Cd
2+and Pb
2+stripping peak current carry out record.Experimental result shows (Fig. 4), and single chitosan-modified electrode (curve b) is starkly lower than the multiple modified electrode (curve d) of shitosan-graphene quantum dot/bismuth ion to the Detection results of metallic ion.Comparative example three:
Shitosan-graphene quantum dot (without bismuth film modified electrode) is to Zn
2+, Cd
2+and Pb
2+implement to detect to comprise following step simultaneously:
(1) by graphene quantum dot-Chitosan Composites ultrasonic disperse in ultrapure water, the dispersant liquid drop pipetting 5 μ L (2mg/mL) with liquid-transfering gun is applied to glassy carbon electrode surface, at room temperature dry 1h.
(2) this experiment use square wave stripping voltammetry (SWSV) measures the Zn in water
2+, Cd
2+and Pb
2+.Experiment adopts three-electrode system, and wherein working electrode is shitosan-graphene quantum dot compound substance modified glassy carbon electrode (diameter 3mm), and platinized platinum is auxiliary electrode, the three-electrode system that saturated calomel electrode (SCE) is contrast electrode.Shitosan-graphene quantum dot nano composite material modified electrode is placed in 20mL 0.1mol/L NaAc-HAc buffer solution (pH=5.5) (not containing Bi
3+), and in this buffer solution, add certain concentration Zn to be measured
2+, Cd
2+and Pb
2+(300 μ g/L), stirs and enrichment 600s under-1.5V current potential, after static 15s, uses SWSV (-1.4 ~-0.3V) to Zn
2+, Cd
2+and Pb
2+stripping peak current carry out record.Experimental result shows (Fig. 4), and the shitosan-graphene quantum dot compound substance modified electrode (curve c) without bismuth film is starkly lower than shitosan-graphene quantum dot/bismuth ion modified electrode (curve d) to the Detection results of metallic ion.
The present invention detects Zn with shitosan-graphene quantum dot compound substance modified electrode in conjunction with bismuth film electrochemical process simultaneously
2+, Cd
2+and Pb
2+, compared to other detection meanss, preparation method is simple and easy to do, and preparation process is environment friendly and pollution-free, and shitosan-graphene quantum dot/bismuth film modified electrode is for Zn
2+, Cd
2+and Pb
2+can realize simultaneously and highly sensitive detection.
Claims (5)
1. the preparation of shitosan-graphene quantum dot nano composite material and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously
2+, Cd
2+and Pb
2+, it is characterized in that: step is as follows:
A, prepare graphene quantum dot: take after citric acid solid grinds to form white powder and add in crucible, carry out adding thermal response with program control cabinet-type electric furnace.After reaction terminates, take out solid sample, add appropriate ultrapure water, ultrasonic dissolution.After product fully dissolves, suction filtration obtains yellow transparent solution, keeps in Dark Place under normal temperature.
B, prepare shitosan-graphene quantum dot nano composite material: configure certain density chitosan solution, Chitosan powder is dissolved in the acetum of 0.1M, after stirring and dissolving, dropwise add graphene quantum dot solution, Keep agitation in course of reaction, drip sodium hydroxide solution to certain pH value, separating out yellow solid precipitate thing is shitosan-graphene quantum dot nano composite material, freeze drying 24 hours.
C, prepare shitosan-graphene quantum dot nano composite material modified electrode: by graphene quantum dot-Chitosan Composites ultrasonic disperse in ultrapure water, pipette a certain amount of dispersant liquid drop with liquid-transfering gun and be applied to glassy carbon electrode surface, at room temperature dry 1h.
D, electrochemical process detect Zn simultaneously
2+, Cd
2+and Pb
2+: this experiment use square wave stripping voltammetry (SWSV) measures the Zn in water
2+, Cd
2+and Pb
2+.Experiment adopts three-electrode system, and wherein working electrode is the glass-carbon electrode (diameter 3mm) that shitosan-graphene quantum dot compound substance is modified, and platinized platinum is auxiliary electrode, the three-electrode system that saturated calomel electrode (SCE) is contrast electrode.Shitosan-graphene quantum dot nano composite material modified electrode is placed in NaAc-HAc buffer solution (containing bismuth ion/Bi
3+), and in this buffer solution, add certain concentration Pb to be measured
2+, Cd
2+and Zn
2+, stir and enrichment under negative potential, after static, use SWSV to Zn
2+, Cd
2+and Pb
2+stripping peak current carry out record.
2. the preparation of a kind of shitosan-graphene quantum dot nano composite material and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously according to claim 1
2+, Cd
2+and Pb
2+, it is characterized in that: in described step a, citric acid quality is 0.2 ~ 20.0g, temperature of reaction is 100 ~ 300 DEG C, and the reaction time is 0.1 ~ 2h, and during dissolved solid product, ultrapure water used is 2 ~ 20mL.
3. the preparation of a kind of shitosan-graphene quantum dot nano composite material and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously according to claim 1
2+, Cd
2+and Pb
2+, it is characterized in that: in described step b, shitosan solution concentration is 0.2 ~ 20mg/mL, graphene quantum dot solution concentration is 0.2 ~ 20mg/mL, and dripping sodium hydroxide solution is 2 ~ 8 to pH.
4. the preparation of a kind of shitosan-graphene quantum dot nano composite material and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously according to claim 1
2+, Cd
2+and Pb
2+, it is characterized in that: in described step c, liquid-transfering gun pipettes the volume of dispersion liquid is 1 ~ 10 μ L, and concentration is 0.2 ~ 20mg/mL.
5. the preparation of a kind of shitosan-graphene quantum dot nano composite material and its modified electrode are combined with bismuth film and detect Zn by electrochemical process simultaneously according to claim 1
2+, Cd
2+and Pb
2+, it is characterized in that: in described steps d, NaAc-HAc volume of buffer solution is 2 ~ 50mL, concentration is 0.01 ~ 10mol/L; Bi in solution
3+concentration is 100 ~ 10000 μ g/L, Pb
2+, Cd
2+and Zn
2+concentration is 50 ~ 500 μ g/L; Accumulating potential is-2.0 ~-1.0V, and enrichment time is 300 ~ 900s, and rest time is 1 ~ 30s.
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| CN108061748A (en) * | 2017-12-07 | 2018-05-22 | 哈尔滨商业大学 | For detecting the preparation method of the nanometer bismuth oxide graphene composite film electrode of lead ion and cadmium ion |
| CN108061748B (en) * | 2017-12-07 | 2020-03-27 | 哈尔滨商业大学 | Preparation method of nano bismuth trioxide graphene composite membrane electrode for detecting lead ions and cadmium ions |
| CN108918613A (en) * | 2018-06-22 | 2018-11-30 | 江苏大学 | Based on gold nanoparticle/graphite alkene/chitosan trace cadmium ion electrochemical sensor, preparation method and its usage |
| CN111668498A (en) * | 2020-06-30 | 2020-09-15 | 西北师范大学 | Preparation and application of multi-dendritic-crystal Au @ GQDs @ PtPb core-shell-structure nano composite material |
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