CN107632052B - Electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene - Google Patents
Electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene Download PDFInfo
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Abstract
An electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene. The invention belongs to the technical field of electrochemical sensors, and particularly relates to a ferrocene-heteropoly acid/graphene-based electrochemical sensing electrode. The invention aims to solve the problem that no enzyme is used for detecting xanthine at presentThe sensor has the problems of complex preparation, slow response speed and poor sensitivity. The product is as follows: Fc-PMo wrapped by and outside of GCE electrode6W6the/RGO composite membrane; the electrochemical sensor constructed on the basis of the electrochemical sensing electrode has excellent detection performance on xanthine.
Description
Technical Field
The invention belongs to the technical field of electrochemical sensors, and particularly relates to a ferrocene-heteropoly acid/graphene-based electrochemical sensing electrode.
Background
Xanthine is a purine base widely distributed in the organs and body fluids of the human body and other organisms and plays an important role in the process of purine metabolism. The measurement of the content of the xanthine in the blood and tissues of the human body has important value for the diagnosis and treatment of a series of diseases such as gout, hyperuricemia, Parkinson's disease and the like. Xanthine oxide in human tissues readily oxidizes hypoxanthine into xanthine and further into uric acid, during which superoxide radical O is produced2 ·-Accompanied by superoxide,·The increase of the content of OH free radicals, which may lead to the increase of the content of endotoxin, and thus the incidence of the above-mentioned diseases, is a risk signal for the deterioration of the above-mentioned diseases, but the accurate measurement of the content of xanthine can provide an accurate warning of the occurrence of the above-mentioned diseases. Therefore, it is important to find a suitable catalyst to establish a highly sensitive method for detecting xanthine.
Polyacids, as an inorganic active material, have received increasing attention in the field of catalysis due to their excellent electrochemical properties. The excellent electrochemical property is mainly embodied in the oxidation-reduction process that polyacid can not be decomposed under mild conditions and can rapidly and gradually carry out reversible multi-step electron transfer, especially in the catalytic and electrocatalytic processes. Meanwhile, by changing the composition and structure of the polyacid, the electrochemical properties of the polyacid can be changed greatly. Therefore, the polyoxometallate shows great potential application prospect in various researches due to the unique physical and chemical properties of the polyoxometallate. In addition, scientists also find that once the polyacid is deposited on the surface of the electrode, the polyacid can not only solve the problem that the polyacid is easy to dissolve in water and limited in use, but also maintain and enhance the inherent photoelectrochemical properties of the polyoxometallate, which has very important significance in the fields of electrocatalysis and electric sensing.
The graphene is arranged in a honeycomb latticeSp of column2A thin atomic layer of hybridized carbon atoms. Due to the characteristics of high specific surface area, good electronic conductivity, fast electronic transfer, low cost and firm mechanical properties, the graphene becomes a very promising material for the aspects of electrochemical sensors, nano composite materials, batteries, super capacitors and the like. However, graphene nanoplatelets have a tendency to form irreversible agglomerates of each individual sheet in aqueous media through pi-pi and van der waals attraction forces, which can hinder the electrochemical and electrolytic application of graphene. However, recently it has been discovered that poly (diallyldimethylammonium chloride) linear positively charged polyelectrolytes are attractive for non-covalently functionalizing graphene sheets. Poly (diallyldimethylammonium chloride) can be combined with graphene to form a positively charged material without affecting its electronic structure. Therefore, the poly (diallyl dimethyl ammonium chloride) polyelectrolyte and the high-sensitivity graphene are combined to construct a sensor for practical detection, so that the sensor has very important significance.
Ferrocene is known as iron dicyclopentadienyl and has the structure that an iron atom is clamped between two cyclopentadienyl groups. Ferrocene has excellent electrochemical properties and is easily functionalized, and thus is often used for preparing electrode materials of electrochemical sensors. In addition, the unique sandwich structure of ferrocene enables the ferrocene to have stable chemical properties, and the ferrous iron sandwiched in the middle is in an excited state and has multiple valence catalytic properties. Meanwhile, as the aromatic member, ferrocene has the characteristic of easy substitution, different derivatives can be obtained, and monocyclic substitution and bicyclic substitution can be carried out on the ring of the ferrocene, so that various derivatives can be obtained. Therefore, the compound has high redox activity, good biocompatibility and good electron transfer mediator as a biosensor. Ferrocene and its derivatives have been widely used in various fields such as medicine, biology, electrochemistry, etc.
Disclosure of Invention
The invention aims to solve the problems of low detection speed and poor sensitivity of the current enzyme-free sensor for detecting xanthine, and provides an electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene.
The electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene is characterized in that the electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene is formed by a GCE electrode and Fc-PMo wrapped outside the GCE electrode6W6the/RGO composite membrane comprises a GCE electrode and Fc-PMo in sequence from the GCE electrode to the outer layer6W6: a complex layer of ferrocene-phosphomolybdotungstophosphoric acid, RGO: a reduced graphene oxide layer.
In the ferrocene-phosphomolybdotungstic heteropoly acid complex layer, the heteropoly acid is Keggin type phosphomolybdotungstic heteropoly acid with a molecular formula of H3PMo6W6O40·mH2O, m =36 ~ 42, and the mole ratio of ferrocene to heteropoly acid is 1 (6 ~ 8).
The ferrocene-phosphomolybdic tungstic heteropoly acid complex layer is obtained by modifying a GCE electrode in a 10mol/L ~ 12mol/L ferrocene-phosphomolybdic tungstic heteropoly acid solution, and the modification time is 20min ~ 25 min.
The reduced graphene oxide is reduced graphene oxide functionalized by poly (diallyldimethylammonium chloride), and the concentration of the reduced graphene oxide is 4mg/mL ~ 5 mg/mL.
The reduced graphene oxide layer is obtained by modifying a reduced graphene oxide suspension with the concentration of 4mg/L ~ 5mg/L and functionalized by poly (diallyldimethylammonium chloride) through a GCE electrode, and the modification time is 20min ~ 25 min.
The invention has the beneficial effects that:
compared with the traditional enzyme-free sensor, the electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene is constructed. The problems of low detection speed, poor sensitivity and the like in xanthine detection in practical application are solved. The main reason is the synergistic effect of the ferrocene-heteropoly acid and the graphene, namely the transmission rate of electrons on the surface of the electrode is promoted, and the active adsorption sites of small biological molecules on the surface of the electrode are enlarged, so that the electrocatalytic performance of the electrode is greatly improved.
Drawings
FIG. 1 is a drawing ofTest one Fc-PMo on the obtained GCE electrode6W6Scanning electron microscope images of the/RGO composite membrane;
FIG. 2 shows Fc-PMo on GCE electrode obtained in experiment6W6A full spectrum diagram of an X-ray photoelectron spectrum of the/RGO composite membrane in the range of 0 ~ 900 eV;
FIG. 3 is a differential pulse voltammogram of an electrochemical sensor simultaneously catalyzing xanthine oxidation in validation test I; wherein 1 represents a differential pulse voltammogram to which xanthine was added at a concentration of 10. mu.M, 2 represents a differential pulse voltammogram to which xanthine was added at a concentration of 20. mu.M, 3 represents a differential pulse voltammogram to which xanthine was added at a concentration of 30. mu.M, 4 represents a differential pulse voltammogram to which xanthine was added at a concentration of 40. mu.M, and 5 represents a differential pulse voltammogram to which xanthine was added at a concentration of 50. mu.M;
FIG. 4 is a graph showing the response current of the electrochemical sensor to the concentration of added xanthine during the catalysis of xanthine by the electrochemical sensor in test one.
Detailed Description
The first embodiment is as follows: the electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene is characterized in that the electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene is formed by a GCE electrode and an Fc-PMo wrapped outside the GCE electrode6W6the/RGO composite membrane comprises a GCE electrode and Fc-PMo in sequence from the GCE electrode to the outer layer6W6: a complex layer of ferrocene-phosphomolybdotungstophosphoric acid, RGO: a reduced graphene oxide layer.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene is characterized in that in the complex layer of the ferrocene-phosphomolybdotungstic heteropoly acid, the heteropoly acid is Keggin type phosphomolybdotungstic heteropoly acid, and the molecular formula is H3PMo6W6O40·mH2O, m =36 ~ 42, the mole ratio of ferrocene to heteropoly acid is 1 (6 ~ 8), and other steps and parameters are the same as those in the first embodiment.
The third specific embodiment is different from the first specific embodiment or the second specific embodiment in that the ferrocene-phosphomolybdotungstic heteropoly acid complex layer is obtained by modifying a ferrocene-phosphomolybdotungstic heteropoly acid solution with the concentration of 10mol/L ~ 12mol/L by a GCE electrode, and the modification time is 20min ~ 25 min.
Fourth specific embodiment, this specific embodiment is different from the first specific embodiment in that the reduced graphene oxide is a reduced graphene oxide functionalized by poly (diallyldimethylammonium chloride) and has a concentration of 4mg/mL ~ 5mg/mL, and other steps and parameters are the same as those of the first specific embodiment in the third specific embodiment.
Fifth embodiment is different from the first to fourth embodiments in that the reduced graphene oxide layer is obtained by modifying a reduced graphene oxide suspension functionalized by poly (diallyldimethylammonium chloride) at a concentration of 4mg/L ~ 5mg/L with a GCE electrode, and the modification time is 20min ~ 25 min.
The sixth specific implementation mode: the preparation method of the electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene in the embodiment is carried out according to the following steps.
Firstly, preparing ferrocene-phosphomolybdotungstic heteropoly acid solution, namely, dispersing solid phosphomolybdotungstic heteropoly acid into 8mL ~ 10mL distilled water, magnetically stirring for 3min ~ 5min at room temperature with the rotating speed of 50r/min ~ 60r/min, secondly, adding 0.6mL ~ 1mL ferrocene solution into the first step, and changing the color of the solution from bright yellow to dark green to obtain the ferrocene-phosphomolybdotungstic heteropoly acid solution which is marked as Fc-PMo6W6A solution;
in the first step, the molar concentration of the phosphomolybdotungstic heteropoly acid is 10mM ~ 11 mM;
in the first step, the ferrocene molar concentration is 8mM ~ 10 mM;
in the first step, the molar ratio of the ferrocene to the phosphomolybdic tungstic heteropoly acid is 1 (6 ~ 8).
Firstly, simultaneously dripping an ascorbic acid solution and a poly (diallyldimethylammonium chloride) solution into 20ml of magnetically stirred graphene oxide suspension solution at room temperature, wherein the dripping speed is 2 drops/s ~ 4 drops/s, the magnetically stirred speed is 40r/min ~ 50r/min, and the reaction is maintained at room temperature for 20h ~ 24h to obtain the poly (diallyldimethylammonium chloride) -functionalized reduced graphene oxide suspension, namely RGO suspension;
in the second step, the molar concentration of the ascorbic acid in the graphene oxide suspension solution is 10mM ~ 12 mM;
in the second step, the concentration of poly (diallyl dimethyl ammonium chloride) in the graphene oxide suspension solution is 1mg/mL ~ 3 mg/mL;
and in the second step, the concentration of the graphite oxide in the graphene oxide suspension is 4mg/mL ~ 5 mg/mL.
Thirdly, preparing the electrochemical sensing electrode based on the ferrocene-heteropoly acid/graphene, namely immersing the GCE electrode in the ferrocene and phosphomolybdic tungsten heteropoly acid solution obtained in the first step for 20min ~ 25min, taking out the GCE electrode, washing the GCE electrode with deionized water, and then washing the GCE electrode with N2Blow drying, immersing in RGO suspension obtained in step two, soaking for 20min ~ 25min, taking out, washing with deionized water, and washing with N2Drying by blowing to obtain the electrochemical sensing electrode based on the ferrocene-heteropoly acid/graphene, and recording as Fc-PMo6W6A/RGO modified GCE electrode.
The electrochemical sensing electrode prepared by the method has the advantages of simple preparation, quick response and the like, and is sensitive to xanthine detection. The main reason is the synergistic effect of the ferrocene-heteropoly acid and the graphene, namely the transmission rate of electrons on the surface of the electrode is promoted, and the active adsorption sites of small biological molecules on the surface of the electrode are enlarged, so that the electrocatalytic performance of the electrode is greatly improved.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: in the first step, the molar concentration of the phosphomolybdotungstic heteropoly acid is 10.5 mM. Other steps and parameters are the same as those in the sixth embodiment.
The specific implementation mode is eight: the sixth or seventh embodiment is different from the sixth or seventh embodiment in that: in the first step, the ferrocene molar concentration is 9 mM. Other steps and parameters are the same as those of the sixth or seventh embodiment.
The specific implementation method nine: this embodiment differs from one of the sixth to eighth embodiments in that: in the first step, the mole ratio of the ferrocene to the phosphomolybdic tungstic heteropoly acid is 1: 7. other steps and parameters are the same as those in one of the sixth to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the sixth to ninth embodiments in that: dispersing solid phosphomolybdotungstic heteropoly acid into 9mL of distilled water, and magnetically stirring at room temperature for 4min at the rotating speed of 55 r/min; adding 0.8mL of ferrocene solution into the first step, and changing the color of the solution from bright yellow to dark green to obtain the ferrocene-phosphomolybdic tungsten heteropoly acid solution which is marked as Fc-PMo6W6And (3) solution. Other steps and parameters are the same as those in one of the sixth to ninth embodiments.
The concrete implementation mode eleven: this embodiment differs from one of the sixth to tenth embodiments in that: and in the second step, the molar concentration of the ascorbic acid in the graphene oxide suspension solution is 11 mM. Other steps and parameters are the same as those in one of the sixth to tenth embodiments.
The specific implementation mode twelve: this embodiment differs from one of the sixth to eleventh embodiments in that: and in the second step, the concentration of poly (diallyl dimethyl ammonium chloride) in the graphene oxide suspension solution is 2 mg/mL. Other steps and parameters are the same as those in one of the sixth to eleventh embodiments.
The specific implementation mode is thirteen: this embodiment differs from one of the sixth to twelfth embodiments in that: and in the second step, the concentration of graphite oxide in the graphene oxide turbid liquid is 4.5 mg/mL. Other steps and parameters are the same as those in one of the sixth to twelfth embodiments.
The specific implementation mode is fourteen: this embodiment differs from one of the sixth to thirteenth embodiments in that: and secondly, simultaneously dripping an ascorbic acid solution and a poly (diallyldimethylammonium chloride) solution into 20ml of magnetically stirred graphene oxide suspension solution at room temperature, wherein the dripping speed is 3 drops/s, the magnetic stirring speed is 45r/min, and the reaction is maintained at room temperature for 22 hours to obtain the poly (diallyldimethylammonium chloride) -functionalized reduced graphene oxide suspension, namely the RGO suspension. Other steps and parameters are the same as those in one of the sixth to the thirteenth embodiments.
The concrete implementation mode is fifteen: this embodiment differs from one of the sixth to fourteenth embodiments in that: step three, immersing the GCE electrode in the ferrocene and phosphomolybdic tungsten heteropoly acid solution obtained in the step one, immersing for 23min, taking out, washing with deionized water, and then using N2Drying by blowing to obtain a ferrocene-phosphomolybdic tungstic heteropoly acid complex layer; ② immersing the RGO suspension obtained in the step two in the water for 23min, taking out and washing with deionized water, and then using N2Drying by blowing to obtain the electrochemical sensing electrode based on the ferrocene-heteropoly acid/graphene, and recording as Fc-PMo6W6A/RGO modified GCE electrode. Other steps and parameters are the same as those in one of the sixth to the fourteenth embodiments.
The following experiment was performed to verify the effect of the present invention.
The first test and the preparation method of the electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene of the test are carried out according to the following steps.
Firstly, preparing a ferrocene-phosphomolybdic tungsten heteropoly acid solution: dispersing solid phosphomolybdotungstic heteropoly acid into 9mL of distilled water, and magnetically stirring for 4min at room temperature at the rotating speed of 55 r/min; adding 0.8mL of ferrocene solution into the first step, and changing the color of the solution from bright yellow to dark green to obtain the ferrocene-phosphomolybdic tungsten heteropoly acid solution which is marked as Fc-PMo6W6A solution;
in the first step, the molar concentration of the phosphorus-molybdenum-tungsten heteropoly acid is 10.5 mM;
in the first step, the ferrocene molar concentration is 9 mM;
in the first step, the mole ratio of the ferrocene to the phosphomolybdic tungstic heteropoly acid is 1: 7.
secondly, preparing a reduced graphene oxide suspension functionalized by poly (diallyldimethylammonium chloride): dripping an ascorbic acid solution and a poly (diallyldimethylammonium chloride) solution into 20ml of magnetically stirred graphene oxide suspension solution at room temperature, wherein the dripping speed is 3 drops/s, the magnetic stirring speed is 45r/min, and the reaction is maintained for 22 hours at room temperature to obtain poly (diallyldimethylammonium chloride) -functionalized reduced graphene oxide suspension, namely RGO suspension;
in the second step, the molar concentration of ascorbic acid in the graphene oxide suspension solution is 11 mM;
in the second step, the concentration of poly (diallyl dimethyl ammonium chloride) in the graphene oxide suspension solution is 2 mg/mL;
and in the second step, the concentration of graphite oxide in the graphene oxide turbid liquid is 4.5 mg/mL.
Thirdly, preparing the electrochemical sensing electrode based on the ferrocene-heteropoly acid/graphene: immersing a GCE electrode in the ferrocene and phosphorus-molybdenum-tungsten heteropoly acid solution obtained in the step one for 23min, taking out, washing with deionized water, and then using N2Drying; ② immersing the RGO suspension obtained in the step two in the water for 23min, taking out and washing with deionized water, and then using N2Drying by blowing to obtain the electrochemical sensing electrode based on the ferrocene-heteropoly acid/graphene, and recording as Fc-PMo6W6A/RGO modified GCE electrode.
(one) Fc-PMo on GCE electrode obtained in test one6W6Performing morphology characterization on/RGO composite membrane
Experiments as shown in FIG. 1-Fc-PMo on GCE electrodes obtained6W6Scanning electron microscope images of/RGO composite membranes. From FIG. 1, PMo can be seen6W6And the complex is tightly combined with Fc, and the complex has a rod-like structure and is distributed on the graphene nano-sheet more uniformly.
(II) utilizing an X-ray photoelectron spectrometer to perform Fc-PMo on the GCE electrode obtained in the first test6W6Characterization of the/RGO composite membranes yielded Fc-PMo on GCE electrodes obtained as test one shown in FIG. 26W6The full spectrum of X-ray photoelectron spectrum of the/RGO composite membrane in the range of 0 ~ 900eV is obtained according to the XPS chart showing Fe, P,The peak positions of Mo, W and C elements are known as Fc and PMo6W6RGO was successfully bound to the composite membrane.
(III) verification of the Fc-PMo obtained in experiment one of the present application6W6Sensing performance of/RGO modified GCE electrodes.
Preparation of electrochemical sensor
Fc-PMo obtained by the test one of the present application6W6The GCE electrode modified by the/RGO composite membrane is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the platinum wire electrode is used as an auxiliary electrode, and the formed three-electrode system is the electrochemical sensor.
Secondly, the electrochemical sensor obtained in the step one is used for detecting xanthine
And (4) conclusion: obtaining a differential pulse voltammogram of the electrochemical sensor shown in fig. 3 catalyzing xanthine in 0.1M PBS (pH =6) and a graph of response current shown in fig. 4 as a function of added xanthine concentration; wherein 1 in FIG. 3 represents a differential pulse voltammogram to which xanthine was added at a concentration of 10. mu.M, 2 represents a differential pulse voltammogram to which xanthine was added at a concentration of 20. mu.M, 3 represents a differential pulse voltammogram to which xanthine was added at a concentration of 30. mu.M, 4 represents a differential pulse voltammogram to which xanthine was added at a concentration of 40. mu.M, and 5 represents a differential pulse voltammogram to which xanthine was added at a concentration of 50. mu.M. As can be seen from FIG. 3, an irreversible oxidation peak, i.e., the catalytic potential of xanthine, appeared at 0.78V after addition of xanthine, and the catalytic peak current value at 0.78V catalytic potential also uniformly increased linearly with increasing concentration of xanthine (as shown in FIG. 4). This is Fc-PMo6W6The peak current of the/RGO composite membrane is correspondingly changed due to the catalytic oxidation reaction of xanthine. Thus, further elucidating the Fc-PMo6W6The electrochemical sensor constructed on the basis of the/RGO composite membrane has good performance for detecting xanthine.
In conclusion, an electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene is successfully prepared, and an electrochemical sensor constructed on the basis of the sensing electrode has excellent sensing performance on xanthine.
Claims (1)
1. The electrochemical sensing electrode based on ferrocene-heteropoly acid/graphene is characterized in that a GCE electrode and Fc-PMo wrapped outside the GCE electrode6W6the/RGO composite membrane comprises a GCE electrode and a plurality of layers from the GCE electrode to the outer layer in sequence: complex layer of ferrocene-phosphomolybdotungstic heteropoly acid, Fc-PMo6W6And a reduced graphene oxide layer, RGO;
the preparation method of the electrochemical sensing electrode based on the ferrocene-heteropoly acid/graphene comprises the following steps:
firstly, preparing a ferrocene-phosphomolybdic tungsten heteropoly acid solution: dispersing solid phosphomolybdotungstic heteropoly acid into 9mL of distilled water, and magnetically stirring for 4min at room temperature at the rotating speed of 55 r/min; adding 0.8mL of ferrocene solution into the first step, and changing the color of the solution from bright yellow to dark green to obtain the ferrocene-phosphomolybdic tungsten heteropoly acid solution which is marked as Fc-PMo6W6A solution;
in the first step, the molar concentration of the phosphorus-molybdenum-tungsten heteropoly acid is 10.5 mM;
in the first step, the ferrocene molar concentration is 9 mM;
in the first step, the mole ratio of the ferrocene to the phosphomolybdic tungstic heteropoly acid is 1: 7;
secondly, preparing a poly (diallyldimethylammonium chloride) functionalized reduced graphene oxide suspension: simultaneously dripping an ascorbic acid solution and a poly (diallyldimethylammonium chloride) solution into 20ml of magnetically stirred graphene oxide suspension solution at room temperature, wherein the dripping speed is 3 drops/s, the magnetic stirring speed is 45r/min, and the reaction is maintained for 22 hours at room temperature to obtain a poly (diallyldimethylammonium chloride) -functionalized reduced graphene oxide suspension which is marked as RGO suspension;
in the second step, the molar concentration of ascorbic acid in the graphene oxide suspension solution is 11 mM;
in the second step, the concentration of poly (diallyldimethylammonium chloride) in the graphene oxide suspension solution is 2 mg/mL;
in the second step, the concentration of graphite oxide in the graphene oxide turbid liquid is 4.5 mg/mL;
thirdly, preparing the electrochemical sensing electrode based on the ferrocene-heteropoly acid/graphene: immersing a GCE electrode in the ferrocene and phosphorus-molybdenum-tungsten heteropoly acid solution obtained in the step one for 23min, taking out, washing with deionized water, and then using N2Drying; ② immersing the RGO suspension obtained in the step two in the water for 23min, taking out and washing with deionized water, and then using N2Drying by blowing to obtain the electrochemical sensing electrode based on the ferrocene-heteropoly acid/graphene, and recording as Fc-PMo6W6A/RGO modified GCE electrode.
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