CN103940882A - Sensor for detecting trace copper ions in water sample and construction method thereof - Google Patents
Sensor for detecting trace copper ions in water sample and construction method thereof Download PDFInfo
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- CN103940882A CN103940882A CN201410156166.2A CN201410156166A CN103940882A CN 103940882 A CN103940882 A CN 103940882A CN 201410156166 A CN201410156166 A CN 201410156166A CN 103940882 A CN103940882 A CN 103940882A
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- carbon nano
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- walled carbon
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Abstract
The invention discloses a sensor for detecting trace copper ions in a water sample, and a construction method thereof. The surface of an indium tin oxide (ITO) electrode is modified by a great number of sodium phytate functionalized carbon nano tubes by a self-assembly method, so that a net structure formed by the carbon nano tubes in a staggered way can be formed, and large superficial area is provided for depositing metal ions. Furthermore, sodium phytate exposed on the surfaces of the carbon nano tubes contains a great number of phosphate groups, the metal ions in the water sample can be easily captured by the phosphate groups, and complexes can be formed by the phosphate groups and the metal ions; the prepared electrode has good response to the copper (II) ions, and has the advantages of being low in limit of detection, high in sensitivity, good in selectivity and the like; therefore, the sensor is excellent in detection on the metal copper ions in the water sample. Furthermore, the preparation method is simple, environmentally friendly and low in cost.
Description
Technical field
The invention belongs to a kind of " environment is green " had to higher ligand stability constant phytic acid sodium salt to copper ion for the preparation of trace copper ion sensor in water sample.
Background technology
Copper is that underwater gold belongs to a kind of of element, is that human body is requisite, but excessive copper is very large to the harm of human body.Free state copper ion is more much bigger than coordinating state copper to the harm of human body.Excessive copper ion has great negative interaction to many hydrobionts, and cause is that its sulfydryl in protein is combined, and disturbs the activity of sulfydryl enzyme, if as there being excessive copper ion in the ecological tanks such as coral, pasture and water, will make very soon loved biology get killed.The pollution of copper is mainly derived from the industries such as plating, metallurgy, chemical industry.Think in time, the quality of monitor water, guarantee that people obtain safe drinking water, the mensuration of content of copper ion in water body is had very important significance.The technology that detects at present heavy metal mainly contains spectroscopic methodology and electrochemical process, and spectroscopic methodology comprises atomic absorption spectrography (AAS), atomic emission spectrometry, atomic fluorescence method, mass spectroscopy etc.; Electrochemical process comprises voltammetry, polarography, potentiometry, conductimetry etc.In recent years, studying more is to use anodic stripping voltammetry to detect heavy metal ion, and it is a kind of very sensitive analytical approach, and detectability can reach 10
-11mol L
-1.Meanwhile, at present copper ion is detected to more research and focus on a kind of modified electrode that can specific recognition to metallic ion of preparation.The selectivity recognition material that is generally usually used in chemically modified electrode has crown ether, cyclodextrin, and calixarenes, halfcystine, Phen and derivant thereof, shitosan and disodium EDTA etc., these compounds have stronger complexing power to metallic ion.But most of can the pollution environment generation of decorative material that these modified electrodes are used, or be these modified electrode more complicated of preparation.Therefore, how when accurately being detected, metal copper ion to there is high sensitivity, high selectivity, and sensor is nontoxic simultaneously, and environmentally safe and preparation method are simple, will be the targets that researchers constantly struggle for it.Carbon on multi-walled carbon nano-tubes
atomp electronics form large-scale delocalized pi-bond, because conjugative effect is remarkable, multi-walled carbon nano-tubes has good electric conductivity, and its specific surface area is large, is considered to good conducting polymer composite material.Sodium phytate has stronger water wettability, and better biocompatibility, nontoxic, environmentally friendly, has six phosphoric acid ester bonds in its structure, copper ion had to very strong coordination ability and carbon nano-tube hydrophobic in water is had to good dispersibility simultaneously.By the functionalized multi-walled carbon nano-tubes of sodium phytate, prepare modified electrode compound substance, the electrode that this compound substance is modified has possessed the good electric conductivity of carbon nano-tube, the character such as coordination ability that larger specific surface area and sodium phytate are stronger to copper ion, have realized metal copper ion high sensitivity and highly selective have been detected in conjunction with anodic stripping voltammetry simultaneously in this.
Up to now, at home and abroad there is no metal copper ion sensor in detection water sample prepared by utilization " green " phytic acid sodium salt.So it is low to invent a kind of detectability, highly sensitive, the sensor of the detection copper ion that selectivity is good is an important technological problems in the urgent need to address.
Summary of the invention
The object of this invention is to provide a kind of detectability low, highly sensitive, the sensor of trace copper ion in the good detection water sample of selectivity.
The object of the present invention is achieved like this:
A construction method for trace copper ion sensor in water sample, comprises the following steps:
(1) take multi-walled carbon nano-tubes, adding the concentrated sulphuric acid and red fuming nitric acid (RFNA) volume ratio is the nitration mixture of 3:1, and ultrasonic 4～4.5 hours, dilution, filtered, and washing, to neutral, is drying to obtain the multi-walled carbon nano-tubes of activation; The amount ratio of multi-walled carbon nano-tubes and nitration mixture is 2.5-6.5g/mL;
(2) it is 1.0 * 10 that the multi-walled carbon nano-tubes activating joins concentration according to the ratio of 1mg/mL
-2in the sodium phytate solution of mol/L, ultrasonicly mix 7～8 hours, obtain the functionalized multi-walled carbon nano-tubes suspending liquid of sodium phytate of stable uniform;
(3) by ITO(indium oxide tin glass) after electrode clean activation, control ITO conductive area 1cm * 1cm, nail polish is coated with envelope for all the other areas, dries, standby;
(4) the ITO electrode having dried is immersed in the functionalized multi-walled carbon nano-tubes suspending liquid of sodium phytate, in 4 ℃ of refrigerators, self assembly is three hours, then, takes out, and by washed with de-ionized water, makes sodium phytate functionalized carbon nanotubes and modifies ITO electrode.
Environmentally friendly reagent sodium phytate (Na-IP
6), have another name called sodium phytate, in the structure of its molecule, contain 6 non-coplanar phosphoric acid ester bonds, make it have the ability of very strong chelated polyvalent metal ion, itself and the coordination ratio of copper (II) ion and the coordination of other metallic ions are stable.Sodium phytate is a kind of important fully natural green adjuvant, and the most significant feature is to have extremely strong huge legendary turtle cooperation use with metallic ion, stronger inoxidizability and protect look.Be widely used in the anti-oxidant and color stabilizer of fruit-vegetable juice beverage, meat products, marine product.Mainly to carry out functionalized multi-walled carbon nano-tubes with sodium phytate herein, sodium phytate is adsorbed on to the surface of carbon nano-tube, utilize sodium phytate easily and ITO surface have stronger effect, adopt self-assembling technique, will be a large amount of carbon nano tube modified to ITO electrode surface, thereby form the staggered reticulate texture of carbon nano-tube, for plated metal ion provides a large amount of surface areas.Simultaneously, be exposed to the sodium phytate of carbon nano tube surface, contain a large amount of bound phosphate groups, easily catch the metal copper ion in water sample and form with it complex compound, preparing electrode pair copper (II) ion has good response, and it is low to have detectability, highly sensitive, good selective is the sensor of metal copper ion in a kind of good detection water sample.
The present invention adopts self-assembling method, and a large amount of sodium phytate functionalized carbon nanotubes are modified to ITO electrode surface, thereby forms the staggered reticulate texture of carbon nano-tube, for plated metal ion provides a large amount of surface areas.Simultaneously, be exposed to the sodium phytate of carbon nano tube surface, contain a large amount of bound phosphate groups, easily catch the metallic ion in water sample and form with it complex compound, preparing electrode pair copper (II) ion has good response, and it is low to have detectability, highly sensitive, good selective is the sensor of metal copper ion in a kind of good detection water sample.
Advantage of the present invention is:
1, preparation method is simple, environmental protection, and cost is low.
2, the coordination ratio of phytic acid sodium salt and Cu (II) ion and the coordination of other metallic ions are stable, and the phytic acid sodium salt of therefore modifying on ITO electrode improves preferably the selectivity of electrode pair copper ion in anodic stripping voltammetry process.
3, detectability is low, highly sensitive.
Accompanying drawing explanation
Fig. 1 is sensor preparation process figure.
Fig. 2 is FESEM figure and the IP that multi-walled carbon nano-tubes is modified ITO electrode and sodium phytate functionalized carbon nanotubes modification ITO electrode
6the XPS of-MWCNTs-ITO electrode characterizes.
Fig. 3 is that Different electrodes is to 0.01mol L
-1cuCl
2the cyclic voltammetry curve figure of response.
Fig. 4 is that sensor of interest is to the conventional pulsed anode Stripping Voltammetry of the differential of variable concentrations Cu (II) ion figure.
Embodiment
Below by embodiment, the present invention will be further described.
Electrochemistry experiment of the present invention carries out on CHI660D type electrochemical workstation (Shanghai Chen Hua Instrument Ltd.); Field emission scanning electron microscope spectrum adopts Hitachi S – 4800 (Tokyo, Japan) field emission scanning electron microscope, and other instruments are FE20 laboratory pH meter (plum Teller-Tuo benefit instrument Shanghai company limited); SK2200H Ultrasound Instrument (Shanghai High Kudos Science Instrument Co., Ltd.).
IP6-MWCNTs-ITO electrode production process as shown in Figure 1.Phytate functionalized carbon nanotubes is modified the preparation method that ITO prepares trace copper ion sensor in water sample: take the multi-walled carbon nano-tubes of 0.9～1.5 gram, adding the concentrated sulphuric acid and red fuming nitric acid (RFNA) volume ratio is the nitration mixture 24mL of 3:1, ultrasonic 4～4.5 hours, then, dilution, filter, washing, to neutral, is drying to obtain the multi-walled carbon nano-tubes of activation.It is 1.0 * 10 that the multi-walled carbon nano-tubes of 0.017～0.02g activation is joined to 17～20mL concentration
-2in the sodium phytate solution of mol/L, ultrasonicly mix 7～8 hours, just obtain the functionalized multi-walled carbon nano-tubes suspending liquid of sodium phytate of stable uniform.By after the activation of ITO electrode clean, control ITO conductive area 1cm * 1cm, all the other areas are coated with envelope with nail polish, dry, standby.The ITO electrode having dried is immersed in the functionalized multi-walled carbon nano-tubes suspending liquid of sodium phytate, and in 4 ℃ of refrigerators, self assembly is three hours, then, takes out, and by washed with de-ionized water, makes sodium phytate functionalized carbon nanotubes and modifies ITO electrode.
Field emission scanning electron microscope (FESEM) is a kind of effective means of Electrode surface microscopic topographic.X-ray photoelectron power spectrum is a kind of conventional surface composition analytical approach at present.Fig. 2 utilizes field emission scanning electron microscope and the sign of x-ray photoelectron power spectrum to the modification ITO electrode of preparation.Fig. 2 A does not have the functionalized carbon nano-tube of sodium phytate to self-assemble to the FESEM figure of the modified electrode of ITO, can see that the carbon nano-tube of only having is seldom assembled into ITO electrode surface; Fig. 2 B is the FESEM figure that the functionalized carbon nano-tube of sodium phytate self-assembles to ITO modified electrode, can see that a large amount of carbon nano-tube is assembled in ITO electrode surface, forms staggered reticulate texture.Thus, illustrate that the functionalized carbon nano-tube of sodium phytate is more prone to be assembled into ITO electrode surface, and larger specific surface area is provided.Fig. 2 C is the x-ray photoelectron energy spectrogram to IP6-MWCNTs-ITO electrode, finds that the 2P orbital electron that occurs P elements at electron binding energy 133.5eV, in conjunction with peak, has proved the existence of sodium phytate thus.
Fig. 3 is respectively naked ITO electrode, and multi-walled carbon nano-tubes modifies ITO electrode and the functionalized multi-walled carbon nano-tubes of sodium phytate is modified ITO electrode pair 0.01mol L
-1cuCl
2the cyclic voltammetry curve figure of response.Curve (a) is the response cycle volt-ampere curve figure of naked ITO electrode pair copper ion, can be observed respectively the oxidation peak that occurs copper ion at current potential 0.40V and 0.72V by figure; Curve (b) is the cyclic voltammetry curve figure that sodium phytate functionalized carbon nanotubes is modified the response of ITO electrode pair copper ion, can observe the oxidation peak that only occurs copper ion at current potential 0.29V; Curve (c) is the cyclic voltammetry curve figure that multi-walled carbon nano-tubes is modified the response of ITO electrode pair copper ion, can observe respectively the oxidation peak that occurs copper ion at current potential 0.32V and 0.59V.The cyclic voltammetry curve figure that compares three kinds of electrodes, can find out, the functionalized multi-walled carbon nano-tubes of sodium phytate is modified ITO electrode and is had the lower current potential of copper ion oxidation and higher response current, and there is background interference still less, show the superiority of IP6-MWCNTs-ITO electrode pair copper (II) ion detection.
Next be the performance parameter that adopts this sensor of investigation of the conventional pulsed anode Stripping Voltammetry of differential standard measure.Fig. 4 is that IP6-MWCNTs-ITO electrode is under the operating potential of current potential-0.5V, at the 0.05mol of pH=3.00 L-1KNO
3in solution, adopt the CuCl of i-t curve deposition variable concentrations
2, then adopt the conventional pulse voltammetry of differential ,-0.5V-0.5V potential range stripping copper.Along with the concentration increase of copper ion, oxidation peak current and peak area increase gradually.Interior illustration has reflected this sensor linearity correction relation to oxidation peak area under different Cu (II) ion concentration, the concentration of finding out response peak area and Cu (II) ion is linear, in 1.00 * 10-8～1.00 * 10-6mol L-1 scope, linear regression coeffficient 0.9976, lowest detection is limited to 2.50 * 10-9mol L-1(signal to noise ratio (S/N ratio) S/N=3).By same procedure, prepare five IP6-MWCNTs-ITO electrodes, same concentration Cu (II) solution (0.06 μ mol L-1) is measured, relative standard deviation (R.S.D.) is 3.2%.This shows that IP6-MWCNTs-ITO electrode has good reappearance.
Experimental result shows that this sensor has gratifying reappearance and sensitivity.
Table 1 is IP
6-MWCNTs-ITO electrode under each metal ion species of 100 times of concentration excess exists to 1.00 * 10
-6mol L
-1the response current value comparison of Cu (II), shows IP
6-MWCNTs-ITO electricity
Extremely copper (II) ion is had to good selectivity.
Table 1
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have change and change.Within the spirit and principles in the present invention all, any modification of doing, improvement etc., within all should being included in protection scope of the present invention.
Claims (2)
1. a construction method for trace copper ion sensor in water sample, comprises the following steps:
(1) take multi-walled carbon nano-tubes, adding the concentrated sulphuric acid and red fuming nitric acid (RFNA) volume ratio is the nitration mixture of 3:1, and ultrasonic 4～4.5 hours, dilution, filtered, and washing, to neutral, is drying to obtain the multi-walled carbon nano-tubes of activation; The amount ratio of multi-walled carbon nano-tubes and nitration mixture is 2.5-6.5g/mL;
(2) it is 1.0 * 10 that the multi-walled carbon nano-tubes activating joins concentration according to the ratio of 1mg/mL
-2in the sodium phytate solution of mol/L, ultrasonicly mix 7～8 hours, obtain the functionalized multi-walled carbon nano-tubes suspending liquid of sodium phytate of stable uniform;
(3) by after the activation of ITO electrode clean, control ITO conductive area 1cm * 1cm, all the other areas are coated with envelope with nail polish, dry, standby;
(4) the ITO electrode having dried is immersed in the functionalized multi-walled carbon nano-tubes suspending liquid of sodium phytate, in 4 ℃ of refrigerators, self assembly is three hours, then, takes out, and by washed with de-ionized water, makes sodium phytate functionalized carbon nanotubes and modifies ITO electrode.
2. a trace copper ion sensor in water sample, is characterized in that, method preparation according to claim 1.
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Cited By (4)
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| CN105466988A (en) * | 2015-11-20 | 2016-04-06 | 河南理工大学 | An amino-functionalized ionic liquid-carbon nanotube based copper ion selective electrode and a preparing method thereof |
| CN106018532A (en) * | 2016-06-13 | 2016-10-12 | 山东省科学院新材料研究所 | Preparation of graphene oxide and phytate modified electrode and electrochemical detection device assembled by graphene oxide and phytate modified electrode |
| CN106525931A (en) * | 2016-09-28 | 2017-03-22 | 中国科学院长春应用化学研究所 | Detection method of copper ion concentration in solution |
| CN106568751A (en) * | 2016-11-01 | 2017-04-19 | 广西壮族自治区林业科学研究院 | CNTs-modified 1,4-dioxyanthraquinone doped cellulose-combined porous membrane and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105466988A (en) * | 2015-11-20 | 2016-04-06 | 河南理工大学 | An amino-functionalized ionic liquid-carbon nanotube based copper ion selective electrode and a preparing method thereof |
| CN105466988B (en) * | 2015-11-20 | 2018-04-17 | 河南理工大学 | A kind of copper ion selective electrode based on amino functional ionic liquid carbon nanotubes and preparation method thereof |
| CN106018532A (en) * | 2016-06-13 | 2016-10-12 | 山东省科学院新材料研究所 | Preparation of graphene oxide and phytate modified electrode and electrochemical detection device assembled by graphene oxide and phytate modified electrode |
| CN106018532B (en) * | 2016-06-13 | 2019-01-22 | 山东省科学院新材料研究所 | The electrochemical detection device of preparation and the assembling of graphene oxide and phytic acid modified electrode |
| CN106525931A (en) * | 2016-09-28 | 2017-03-22 | 中国科学院长春应用化学研究所 | Detection method of copper ion concentration in solution |
| CN106525931B (en) * | 2016-09-28 | 2018-10-26 | 中国科学院长春应用化学研究所 | The detection method of copper ion concentration in a kind of solution |
| CN106568751A (en) * | 2016-11-01 | 2017-04-19 | 广西壮族自治区林业科学研究院 | CNTs-modified 1,4-dioxyanthraquinone doped cellulose-combined porous membrane and preparation method and application thereof |
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