CN106290534A - A kind of optimization method of detection of heavy metal ion based on graphene oxide - Google Patents
A kind of optimization method of detection of heavy metal ion based on graphene oxide Download PDFInfo
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- CN106290534A CN106290534A CN201510235658.5A CN201510235658A CN106290534A CN 106290534 A CN106290534 A CN 106290534A CN 201510235658 A CN201510235658 A CN 201510235658A CN 106290534 A CN106290534 A CN 106290534A
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Abstract
The invention discloses the optimization method of a kind of detection of heavy metal ion based on graphene oxide, it comprises the steps of and is disperseed in a solvent by graphene oxide, obtain graphene oxide dispersion, by knife coating graphene oxide is coated with on an enclosure for storing grain substrate and is prepared as electrode；Again by electrodeposition process, at the electrode surface deposition polyaniline prepared, and test as working electrode.Present invention, avoiding use complex configuration in current graphene oxide sensing technology, simplify Fabrication Technology of Electrode, improve detection sensitivity, it is achieved that the acidifying of a kind of novel simple optimizes technique.
Description
Technical field
The present invention relates to the acidifying optimisation technique of a kind of heavy metal ion Electrochemical Detection based on graphene oxide, belong to chemical analysis or sensor measuring technical field.
Background technology
In recent decades along with developing rapidly of China's economic and going deep into of process of industrialization, heavy metal and compound thereof pollute the various aspects having jeopardized the human lives such as water quality, air and food.Heavy metal contaminants not only strong toxicity, easily it is enriched with, and can not be biodegradable, especially the health of the aspects such as digestive system, nervous system and the blood circulation of the mankind is constituted serious threat.For example, lead ion (Pb2+) can cause nauseating, twitch, the symptom such as renal failure and cancer, copper ion (Cu2+) then can cause the clinical symptoms such as hemochromatosis, gastrointestinal mucosa inflammation, leg cramp, dermatosis, chromium ion (Cr2+) especially severe toxicity carcinogen, therefore, its content in drinking water of Environmental Protection in America mechanism considered critical must not exceed 100mg/L.Mercury ion (Hg2+), it is commonly called as hydrargyrum, even if the dosage of trace can also cause renal failure and respiratory failure, thus causes absorption person dead.According to incompletely statistics, the most at least 10000 tons of heavy metal elements are released in human habitat.
Electrochemical measuring technique is because measurement sensitivity is higher, easy and simple to handle, and detection speed is fast, and the green technology of substantially environmentally safe, receive the extensive attention of domestic and international researcher.When as a kind of detection of heavy metal ion technology, its effect is limited by specific surface area and the effective detection range of sensing material.The physically and electrically chemical property of graphene-based material uniqueness is (such as bipolarity, high conductivity, high-specific surface area, high mechanical properties, low electronic noise, easy sense dough etc.), sensing material as exploitation heavy metal ion detector/sensor has some oxygen-containing functional groups in good prospect, particularly graphene oxide, such as hydroxyl and carboxyl.Defect that this material surface has and the substantial amounts of active center that functionalization group produces, this greatly enhances the adsorption of graphenic surface heavy metal ion, if the polyaniline at the surface of graphene oxide deposition dendritic structure can also increase avtive spot further.More worth one is mentioned that, the effective detection range of graphene oxide can reach 30nm, is 5 times of tradition sensing material, and this modifies also to its surface and provides bigger performance space.Present invention utilizes the polyaniline of surface of graphene oxide deposition, not only increase the enriched site of heavy metal ion, and the metallic character that polyaniline shows under strongly acidic conditions enhances electronic transmission performance, thus promote the sensitivity of Detection Techniques.
Summary of the invention
The technical problem to be solved in the present invention is the optimization for the detection of heavy metal ion built based on graphene oxide, it is provided that a kind of method improving detection sensitivity simple, effective.The metallic character specifically utilizing polyaniline to show under strongly acidic conditions, the transmission of electronics of being more convenient for, improve detection limit.
The purpose of the present invention implements the most by the following technical programs:
1) the preparation neutral conductive solution of 0.05-0.15M and the aniline solution of 1-10 μM, be added thereto to hac buffer and strong acid respectively；
2), by graphene oxide powder ultrasonic, after being uniformly dispersed, blade coating equipment is prepared the graphene oxide electrode of 1-10 micron thickness, and 60 DEG C of drying in vacuum drying oven；
3) 10 × 10mm step 2 is cut) the middle electrode prepared, utilize cyclic voltammetry to deposit polyaniline on its surface；
4) graphene oxide of the surface prepared in step 3) deposition polyaniline is put into conducting solution to be detected, test under regulation pH value of solution to strong acidic condition.
Accompanying drawing explanation
Accompanying drawing is for providing a further understanding of the present invention, and constitutes a part for description, is used for explaining the present invention, is not intended that limitation of the present invention together with the example of the present invention.In the accompanying drawings:
Fig. 1 graphene oxide electrode (5 μm) Pb under condition of different pH2+Detection results
Fig. 2 graphene oxide electrode (10 μm) Pb under condition of different pH2+Detection results
Detailed description of the invention
Following preferable examples of the present invention will be described, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains principle and the essence of the present invention, is not intended to limit the present invention.
The present invention provides the optimization technique of a kind of detection of heavy metal ion built based on graphene oxide, and described method comprises the steps:
1) the preparation neutral conductive solution of 0.05-0.15M and the aniline solution of 1-10 μM, be added thereto to certain density hac buffer and strong acid respectively；
2), by graphene oxide powder ultrasonic, after being uniformly dispersed, the graphene oxide electrode that thickness is 1-10 μm, and 60 DEG C of drying in vacuum drying oven are prepared on flexible substrates with knife coating；
3) 10 × 10mm step 2 is cut) the middle electrode prepared, utilize cyclic voltammetry to deposit polyaniline on its surface；
4) graphene oxide of the surface prepared in step 3) deposition polyaniline is put into conducting solution to be detected, test under regulation pH value of solution to strong acidic condition；
Hereinafter each step of the inventive method is described in further detail as follows:
Further describe the present invention by detailed one exemplary embodiment below, but these embodiments do not constitute any limitation of the invention.
Example 1
The KNO of preparation 0.05M3Conducting solution and the aniline solution of 5 μMs, be added thereto to the hac buffer of pH=5.3 and the HCl of 0.1M respectively.By graphene oxide powder ultrasonic, after being uniformly dispersed, in polyethylene terephthalate (PET), prepare, with knife coating, the graphene oxide electrode that thickness is 5 μm, 60 DEG C of drying in vacuum drying oven.Cut the electrode that 10 × 10mm prepares, utilize cyclic voltammetry to scan 30 circulations between-0.2-0.9V, thus deposit polyaniline on its surface.The graphene oxide that the surface of preparation deposits polyaniline is put into conducting solution to be detected, according to pH meter strong acid regulation pH value of solution and tests with Differential Pulse Voltammetry.
It will be seen from figure 1 that along with the reduction Pb of pH2+Characteristic peak intensity more and more obvious, show that acidifying can effectively strengthen the sensitivity of detection.
Example 2
The NaCl conducting solution of preparation 0.15M and the aniline solution of 10 μMs, be added thereto to the hac buffer of pH=6 and the H of 0.5M respectively2SO4.By graphene oxide powder ultrasonic, after being uniformly dispersed, knife coating is utilized to prepare the graphene oxide electrode that thickness is 10 μm on polrvinyl chloride (PVC), 60 DEG C of drying in vacuum drying oven.Cut the electrode that 10 × 10mm prepares, utilize cyclic voltammetry to scan 30 circulations between-0.2-0.9V, thus deposit polyaniline on its surface.The graphene oxide that the surface of preparation deposits polyaniline is put into conducting solution to be detected, according to pH meter strong acid regulation pH value of solution and tests with Square wave anodic stripping voltammetry method.
Figure it is seen that at Pb2+In the case of concentration is constant, characteristic peak intensity is more obvious along with the reduction of pH, shows can effectively strengthen under strong acidic condition the sensitivity of detection.
Claims (8)
1. an acidifying optimization method for the detection of heavy metal ion built based on graphene oxide, specifically comprises the following steps that
1) preparation conducting solution and aniline solution；
2), by graphene oxide powder ultrasonic, after being uniformly dispersed, blade coating equipment is prepared the graphene oxide electrode of specific thicknesses, then 60 DEG C of drying in vacuum drying oven；
3) by step 2) in the electrode of preparation be cut into 10 × 10mm size, and deposit polyaniline on its surface, as the working electrode of test；
4) working electrode prepared in step 3) is put into the conducting solution containing heavy metal ion, test after strong acid regulation pH value of solution.
2. the conducting solution described in claim 1 and the preparation of aniline solution, it is characterised in that: conducting solution includes KNO3、KCl、NaNO3Or NaCl solution, solution concentration is 0.05-0.15M；And it is added thereto to the hac buffer that pH is 5-6；The concentration of aniline solution is 1-10 μM, and is added thereto to HCl or H that concentration is 0.1-0.5M2SO4。
3. the preparation of the graphene oxide electrode described in claim 1, it is characterised in that: described solvent includes deionized water, ethanol or both mixed solutions, ultrasonic uniformly after, by serosity blade coating or be spin-coated in substrate, preferably knife coating.
4. the determination of the pH value described in claim 1-2 is measured by pH meter.
5. graphene oxide described in claim 1,3, it is characterised in that: the flexible substrate such as concentration is 1mg/L 10mg/L, and thickness is 1-10 μm, the preferred polyethylene terephthalate of the substrate (PET) of use, polrvinyl chloride (PVC).
6. the technique of the deposition polyaniline described in claim 1, it is characterised in that: carrying out potential deposition by cyclic voltammetry, cycle potentials is-0.2-0.9V.
7. the detection method described in claim 1, it is characterised in that: detection method can select Square wave anodic stripping voltammetry method, Differential Pulse Voltammetry, preferably Square wave anodic stripping voltammetry method.
8. the method for testing described in claim 1,7, it is characterised in that: using Ag/AgCl as reference electrode, Pt sheet is as auxiliary electrode, and three electrodes lay respectively at three vertex positions of the equilateral triangle that the length of side is 10mm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100133119A1 (en) * | 2007-08-02 | 2010-06-03 | Macpherson Julie Victoria | Nanotube electrochemistry |
| WO2013040190A1 (en) * | 2011-09-16 | 2013-03-21 | The Research Foundation Of State University Of New York | Low concentration ammonia nanosensor |
| CN103983681A (en) * | 2014-05-23 | 2014-08-13 | 湖南大学 | Electrochemical sensor for detecting heavy metals and preparation method and application thereof |
| CN105842318A (en) * | 2016-03-25 | 2016-08-10 | 大连理工大学 | Preparation method and application of graphene/polypyrrole electrochemical sensor for trace-amount lead ion detection |
| CN105928996A (en) * | 2016-06-21 | 2016-09-07 | 山东省科学院新材料研究所 | Preparation of graphene oxide and polyaniline-modified electrode and assembled electrochemical detection device |
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- 2015-05-11 CN CN201510235658.5A patent/CN106290534A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100133119A1 (en) * | 2007-08-02 | 2010-06-03 | Macpherson Julie Victoria | Nanotube electrochemistry |
| WO2013040190A1 (en) * | 2011-09-16 | 2013-03-21 | The Research Foundation Of State University Of New York | Low concentration ammonia nanosensor |
| CN103983681A (en) * | 2014-05-23 | 2014-08-13 | 湖南大学 | Electrochemical sensor for detecting heavy metals and preparation method and application thereof |
| CN105842318A (en) * | 2016-03-25 | 2016-08-10 | 大连理工大学 | Preparation method and application of graphene/polypyrrole electrochemical sensor for trace-amount lead ion detection |
| CN105928996A (en) * | 2016-06-21 | 2016-09-07 | 山东省科学院新材料研究所 | Preparation of graphene oxide and polyaniline-modified electrode and assembled electrochemical detection device |
Non-Patent Citations (1)
| Title |
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| NIPAPAN RUECHA 等: ""Sensitive electrochemical sensor using a graphene–polyaniline nanocomposite for simultaneous detection of Zn(II), Cd(II), and Pb(II)", 《ANALYTICA CHIMICA ACTA》 * |
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