CN107121481A - A kind of working electrode detection micro amount of arsenic of composite modification and the electrochemical method of trace arsenic and heavy metal - Google Patents
A kind of working electrode detection micro amount of arsenic of composite modification and the electrochemical method of trace arsenic and heavy metal Download PDFInfo
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- CN107121481A CN107121481A CN201611118693.XA CN201611118693A CN107121481A CN 107121481 A CN107121481 A CN 107121481A CN 201611118693 A CN201611118693 A CN 201611118693A CN 107121481 A CN107121481 A CN 107121481A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The present invention relates to a kind of working electrode detection micro amount of arsenic of composite modification and the electrochemical method of trace arsenic and heavy metal, belong to the association areas such as food, health, environmental monitoring.The present invention mainly uses common carbon material and g C3N4The composite of formation modifies working electrode, and quantitative analysis measure is carried out to micro and trace arsenic and heavy metal ion by anodic stripping voltammetry.The working electrode of the present invention only needs to use graphene/g C3N4Composite is coated in electrode surface and can directly tested, and adds micro nafion or bismuth ion is added in solution to be measured, can significantly improve the detectable limit of arsenic and heavy metal ion.Electrode modification process simple and fast, sensitivity is high, and performance is stable, can quick detection is micro and trace arsenic and heavy metal ion, have very strong popularizing application prospect.
Description
Technical field
The present invention relates to the electrochemical analysis detection field such as food, health, environment, more particularly to a kind of g-C3N4/ C is multiple
The working electrode detection micro amount of arsenic and the electrochemical method of trace arsenic and heavy metal of condensation material modification.
Background technology
Heavy metal pollution is directly detrimental to health, and causes environmental quality to deteriorate, wherein especially lead, mercury, cadmium, chromium,
Five kinds of harm such as arsenic are maximum.Heavy metal is detected compared to some large-scale instruments, it is e.g., atomic absorption spectrography (AAS), atomic fluorescence method, ultraviolet
Visible spectrophotometry, x ray fluorescence spectrometry, inductively coupled plasma mass spectrometry, electrochemical method substantially have standby letter
Single, easy to operate, the advantages of sensitivity is high is so electrochemical method detection heavy metal has in fields such as food, health, environment
Important application value.
The higher g-C of nitrogen content3N4It is good catalysis material, it is all two-dimensional material that it, which is all, with graphene.Pass through N
, O atom bridging or pi-pi accumulation effect, graphene and g-C3N4New hybrid material can be assembled into.Graphene/g-C3N4
Composite shows enhanced activity in terms of visible light catalytic, but there is not been reported for the detection of heavy metal ion.
This patent is with graphene/g-C3N4Composite detects micro and trace arsenic and a huge sum of money to modify working electrode analysis
Belong to element, material therefor is cheap and easy to get, modification simple and fast, sensitivity is high, performance is stable, has before very strong popularization and application
Scape.
The content of the invention
The purpose of the present invention is for during the current electrochemical method micro and trace arsenic of detection and heavy metal, work is electric
There is provided a kind of graphene/g-C for the deficiency that the practical application of pole selection is present3N4The working electrode detection of composite modification is micro-
Measure the electrochemical method of arsenic and trace arsenic and heavy metal.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of working electrode detection micro amount of arsenic of composite modification and the electrochemical method of trace arsenic and heavy metal, including it is described
Working electrode is graphene/g-C3N4Composite modification, preparation method is as follows:
Graphene/g-C3N4Melamine or urea etc. are dissolved in water by the preparation process of composite, method one, then by than
Example adds the carbon materials such as dilute graphite, graphene oxide, reduced graphene, is sufficiently mixed, and solid material is added into Muffle after drying
Stove is calcined at a certain temperature obtains graphene/g-C3N4Composite.Method two, by melamine or urea and graphite
The carbon materials such as dilute, graphene oxide, reduced graphene mixed grinding, then graphene/g- is obtained by high-temperature calcination in proportion
C3N4Composite.Method three, by g-C3N4The carbon materials such as, graphene oxide dilute with graphite, reduced graphene are mixed in proportion
Grinding obtains graphene/g-C3N4Composite.Graphene/g-C3N4It is added in ethanol, isopropanol or water equal solvent and surpasses
Sound disperses, and can be carried out after drawing the working electrode surface that quantitative dispersant liquid drop is coated onto clean drying of polishing, drying at room temperature
Test, continues to be added dropwise micro nafion to working electrode surface, or adds in solion to be measured bismuth ion, can be with
Improve detection range.The electrode system of described electrochemical detection method includes two electrodes or three-electrode system.
Described electrochemical analysis method includes Differential Pulse Stripping Voltammetry, square wave Stripping Voltammetry using stripping voltammetry
The correlation techniques such as method, Linear Sweep Stripping Voltammetric.
Described detection range is micro and trace arsenic and heavy metal.Wherein, the preferred lead of heavy metal, chromium, mercury, cadmium, copper,
Zinc.
Compared with prior art, the advantage of the invention is that：
1st, working electrode coating material abundance, the urea and the material such as graphite, carbon black, activated carbon in charcoal nitrogen material source is equal
It is common cheap and easy to get.Ultrasound, which is simply mixed, with carbon material in charcoal nitrogen can meet test request, it is not necessary to extra complicated procedures of forming.
2nd, micro nafion is properly added on the working electrode prepared, or is fitted in the solution of material to be detected
As a certain amount of Bi of addition3+, detection range and minimum detection limit can be improved.
3rd, Electrochemical Test Procedure is simple, and the testing time is short, and test limit is low, and multiple element can be detected simultaneously.It can solve the problem that
Electrochemical method quick detection is micro and trace arsenic and the actual application problem of heavy metal.
Embodiment
Below by embodiment, the invention will be further described：
Embodiment 1
It is prepared by working electrode：
Melamine and graphene etc. are mixed according to certain mass ratio, are fully ground after 600 DEG C of calcinings, 3 as a child, cold
But to room temperature.The absolute ethyl alcohol of certain volume is added, ultrasonic disperse ultrasound 40 minutes is sealed standby.Every time using preceding ultrasound 20
Minute, the hanging drop that 6 uL are 15 ug is extracted with microsyringe and is added to glassy carbon electrode surface after polishing, drying is stored at room temperature
2 uL Du Pont's coating solution is added dropwise afterwards（The nafion solution of DuPont 5%）To electrode surface.Add Bi3+Ion and treat sounding lead from
When sub- mol ratio is 20, graphene/g-C3N4During the working electrode detection lead of composite modification, the concentration of lead ion and dissolution
Peak current linear relationship is good, and detection limit is low.
Embodiment 2
It is prepared by working electrode：Add graphene oxide into aqueous solution of urea, ultrasonic dissolution, after 80 DEG C of dryings, be put into Muffle
Stove.550 DEG C are calcined 3 hours, and cooling naturally cools to room temperature.Take 15 ug graphene/g-C3N4The isopropanol of composite is molten
Drop is coated onto on the glass-carbon electrode after polishing, continues to be added dropwise the 2 uL nafion solution of DuPont 5% to electrode surface, natural
It is stand-by after drying.
Electrochemical Detection uses Differential Pulse Stripping Voltammetry, and arrange parameter is as follows：Accumulating potential -0.8V, enrichment time
700s, cushioning liquid is acetic acid/sodium acetate solution of PH=4.5.
Add Bi3+When ion is 20 with lead ion mol ratio to be measured, the working electrode of carbon black modification is in detection heavy metal lead
When, the concentration and dissolution peak current of lead ion are linear, and detection limit is low.
Embodiment 3
It is prepared by working electrode：
G-C is obtained by urea and reduced graphene mixed grinding in proportion, then by high-temperature calcination3N4/ C composite.15
Ug graphenes/g-C3N4On glass-carbon electrode after the aqueous isopropanol drop coating to polishing of composite, continue to be added dropwise 2 uL's
The nafion solution of DuPont 5% is stand-by after natural drying to electrode surface.
Electrochemical Detection uses Differential Pulse Stripping Voltammetry, and arrange parameter is as follows：Accumulating potential -0.8V, enrichment time
700s, cushioning liquid is acetic acid/sodium acetate solution of PH=4.5.
Add Bi3+When ion is 20 with lead ion mol ratio to be measured, the working electrode of carbon black modification is in detection heavy metal lead
When, the concentration and dissolution peak current of lead ion are linear, and detection limit is low.
Embodiment 4
It is prepared by working electrode：
By g-C3N4Mixed grinding obtains g-C in proportion with graphene oxide3N4/ C composite.15 ug graphenes/g-
C3N4On glass-carbon electrode after the ethanol solution drop coating to polishing of composite carbon black, continue that 2 uL DuPont 5% is added dropwise
Nafion solution is stand-by after natural drying to electrode surface.
Electrochemical Detection uses Differential Pulse Stripping Voltammetry, and arrange parameter is as follows：Accumulating potential -1.0V, enrichment time
700s, cushioning liquid is acetic acid/sodium acetate solution of PH=4.5.
Add Bi3+When ion is 20 with chromium ion mol ratio to be measured, the working electrode of carbon black modification is in detection heavy metal lead
When, the concentration and dissolution peak current of chromium ion are linear, and detection limit is low.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (7)
1. a kind of working electrode detection micro amount of arsenic of composite modification and the electrochemical method of trace arsenic and heavy metal, its feature
The decorative material for being working electrode is g-C3N4/ C composite, the preparation method of the working electrode is as follows:
Graphene/g-C3N4Melamine or urea etc. are dissolved in water by the preparation process of composite, method one, then by than
Example adds the carbon materials such as dilute graphite, graphene oxide, reduced graphene, is sufficiently mixed, and solid material is added into Muffle after drying
Stove is calcined at a certain temperature obtains graphene/g-C3N4Composite；Method two, by melamine or urea and graphite
The carbon materials such as dilute, graphene oxide, reduced graphene mixed grinding, then graphene/g- is obtained by high-temperature calcination in proportion
C3N4Composite；Method three, by g-C3N4The carbon materials such as, graphene oxide dilute with graphite, reduced graphene are mixed in proportion
Grinding obtains graphene/g-C3N4Composite；A certain amount of graphene/g-C3N4Composite is added to ethanol, isopropyl
Ultrasonic disperse in alcohol or water equal solvent, sealing preserve is standby；Certain volume is taken to be added drop-wise to glassy carbon electrode surface after polishing, room temperature is done
It is dry.
2. the working electrode detection micro amount of arsenic and trace arsenic and heavy metal of a kind of composite modification according to claim 1
Electrochemical method be characterized in that graphene/g-C3N4The working electrode of composite modification can be in two electrodes or three electrode bodies
System.
3. the working electrode detection micro amount of arsenic and trace arsenic of a kind of composite modification according to claim 1 or 2 and again
The electrochemical method of metal be characterized in that electrochemical analysis method using stripping voltammetry include Differential Pulse Stripping Voltammetry,
The correlation techniques such as square wave stripping voltammetry, Linear Sweep Stripping Voltammetric.
4. the working electrode detection micro amount of arsenic and trace arsenic and again of a kind of composite modification according to claim 1 or 3
The electrochemical method of metal, it is characterised in that the material of carbon material modification working electrode detection is micro and trace arsenic and a huge sum of money
Category.
5. according to claim 1,3 or 4 a kind of composite modification working electrode detection micro amount of arsenic and trace arsenic and
The electrochemical method of heavy metal, it is characterised in that the heavy metal of detection includes：Lead, chromium, mercury, cadmium, copper, zinc etc..
6. a kind of carbon material modification working electrode according to claim 1,2,3,4 or 5 detects micro and trace arsenic and again
The electrochemical method of metal, it is characterised in that the addition concentration of the bismuth ion of detection is：1×10-6 Mol/L~1 × 10-3
mol/L。
7. a kind of carbon material modification working electrode according to claim 1,2,3,4 or 5 detects micro and trace arsenic and again
The electrochemical method of metal, it is characterised in that the nafion of detection（The nafion solution of DuPont 5%）Addition be：1~
1000 uL/mL prepare liquids.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108548860A (en) * | 2018-02-09 | 2018-09-18 | 南昌大学 | Trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene |
| CN108982631A (en) * | 2018-07-26 | 2018-12-11 | 中国科学院山西煤炭化学研究所 | A kind of monatomic metal/composite material of graphene and its preparation method and application |
| CN109781814A (en) * | 2019-01-28 | 2019-05-21 | 暨南大学 | A kind of light enhancing electrochemical sensor and its preparation method and application |
| CN113731458A (en) * | 2020-05-29 | 2021-12-03 | 山东海科创新研究院有限公司 | Graphene/carbon nitride composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103675066A (en) * | 2013-12-18 | 2014-03-26 | 天津工业大学 | Preparation of sulfydryl graphene modified electrode and trace heavy metal detection method thereof |
-
2016
- 2016-12-08 CN CN201611118693.XA patent/CN107121481A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103675066A (en) * | 2013-12-18 | 2014-03-26 | 天津工业大学 | Preparation of sulfydryl graphene modified electrode and trace heavy metal detection method thereof |
Non-Patent Citations (3)
| Title |
|---|
| WENYU GAO ET AL.: "Highly sensitive and selective detection of cadmium with a graphite carbon nitride nanosheets/Nafion electrode", 《RSC ADVANCES》 * |
| 吴敏 等: "石墨烯/铋复合膜修饰玻碳电极检测板蓝根中的铅和镉", 《分析化学》 * |
| 尹竞 等: "g-C3N4/石墨烯复合材料的制备及光催化活性的研究", 《中国环境科学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108548860A (en) * | 2018-02-09 | 2018-09-18 | 南昌大学 | Trivalent arsenic electrochemical detection method based on trithiocyanuric acid/reduced graphene |
| CN108982631A (en) * | 2018-07-26 | 2018-12-11 | 中国科学院山西煤炭化学研究所 | A kind of monatomic metal/composite material of graphene and its preparation method and application |
| CN109781814A (en) * | 2019-01-28 | 2019-05-21 | 暨南大学 | A kind of light enhancing electrochemical sensor and its preparation method and application |
| CN113731458A (en) * | 2020-05-29 | 2021-12-03 | 山东海科创新研究院有限公司 | Graphene/carbon nitride composite material and preparation method and application thereof |
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