CN115165993B - MoSe based on net shape 2 Pt composite material modified electrode and preparation and application thereof - Google Patents
MoSe based on net shape 2 Pt composite material modified electrode and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a MoSe based net shape 2 The Pt composite material modified electrode and the preparation and application thereof are used for sensitively detecting hydrogen peroxide. The invention firstly prepares the netlike MoSe with porous structure by a hard template method 2 Then adopting an in-situ chemical reduction method to directly reduce Pt to net-shaped MoSe 2 Network MoSe with porous structure on surface 2 And the dispersion of Pt is facilitated. The prepared net-shaped MoSe 2 The Pt composite material is mixed with a certain amount of Nafion in an ultrasonic manner to form uniform ink which is dripped on the working electrode, and the modified working electrode is obtained. Taking GCE working electrode as an example, the prepared netlike MoSe 2 Pt non-enzymatic electrochemical hydrogen peroxide sensor pair H 2 O 2 Has high sensitivity, low detection limit and wide detection range. In summary, the invention provides a new material in the field of food and drug detection and has good non-enzymatic electrochemical sensor performance.
Description
Technical Field
The invention belongs to the technical field of analysis detection and electrochemistry, and relates to a network-based MoSe 2 Pt composite material modified electrode and its preparation and application.
Background
Noble metals such as Au, ag and Pt have been used as catalysts for detecting hydrogen peroxide, and particularly Pt is widely used for the preparation of electrochemical biosensing thereof due to its excellent catalytic performance and good electrical conductivity. Pt nanoparticles are typically immobilized on a variety of support materials to further enhance their physical and electrochemical activity, thereby enhancing the performance of electrochemical detection of hydrogen peroxide. However, due to the collision frequency and high surface energy, free noble metal nanoparticles are easy to irreversibly aggregate, noble metals are easy to agglomerate, and the nano-size effect limits the catalytic performance, so that the detection performance and stability of the prepared electrochemical sensor are reduced.
Disclosure of Invention
The first aim of the invention is to overcome the defects of easy agglomeration of noble metal, limited catalytic performance due to nano-size effect and the like in the noble metal electrochemical hydrogen peroxide sensor in the prior art, and provide a network-based MoSe 2 Preparation method of Pt composite material modified electrode.
In order to achieve the above object, the technical solution of the present invention is: preparation of netlike MoSe 2 The electrode is modified by Pt composite material, wherein the electrode takes a glassy carbon electrode as a substrate and is made of netlike MoSe 2 Pt and Nafion were modified by ultrasonic mixing in ethanol, prepared by the following steps:
step (1): preparation of reticulated MoSe by hard template method 2
1-1 preparation of KIT-6 as template:
dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 in a mixed solution of hydrochloric acid and deionized water with a certain concentration, uniformly stirring, adding n-butanol n-BuOH, vigorously stirring, and finally adding TEOS to obtain a mixture; and carrying out hydrothermal treatment on the mixture, collecting white solid, and removing the surfactant through calcination to obtain the KIT-6 template.
1-2 KIT-6 template was reacted with PMA (H 3 PMo 12 O 40 6H 2 O) stirring and mixing in ethanol at room temperature, and obtaining PMA@KIT-6 composite powder after ethanol is completely evaporated;
1-3 mixing the PMA@KIT-6 composite powder with selenium powder, transferring the mixture into a quartz boat, calcining under a hydrogen stream, and finally removing the silica template by using an HF solution.
Step (2): net-shaped MoSe 2 Preparation of Pt composite material:
weighing PtCl with a certain proportion 4 And net-shaped MoSe 2 Adding hydrochloric acid, performing ultrasonic treatment, stirring at a certain temperature until drying, transferring the solid into a hydrogen furnace, calcining, taking out, and crushing to obtain netlike MoSe 2 Pt composite. The PtCl 4 And net-shaped MoSe 2 The molar ratio of (2) is 0.25-1:1.
preferably, the PtCl 4 And net-shaped MoSe 2 The molar ratio of (2) is 1:1.
step (3): preparation of catalyst ink:
the prepared net-shaped MoSe 2 Mixing the Pt composite material with ethanol and perfluorinated sulfonic acid resin Nafion, and performing ultrasonic treatment for more than 1h to prepare catalyst ink with the concentration of 0.01-0.1 g/ml;
preferably, the volume ratio of the perfluorinated sulfonic acid resin Nafion to the ethanol is 0.5-1.5:100.
step (4): polishing and cleaning the glassy carbon electrode;
preferably, in the step (4), a proper amount of alumina powder with the diameter of 0.3 mu m and 0.05 mu m is placed on polishing cloth, a small amount of water is added, the electrodes are sequentially polished into mirror surfaces, the glassy carbon electrodes are respectively immersed into deionized water, ethanol and deionized water for ultrasonic cleaning for 1-2 min, and then the glassy carbon electrodes are immersed in H 2 SO 4 Scanning the solution by cyclic voltammetry until a stable cyclic voltammetry curve is obtained, taking out, washing with deionized water, and using N 2 And drying for standby.
Step (5): dropping the catalyst ink prepared in the step (3) on the surface of the glassy carbon electrode treated in the step (4), and drying in an oven to obtain the netlike MoSe-based catalyst ink 2 The Pt composite material modifies the electrode; wherein the drop amount of the catalyst ink is 3-9 mu L.
Preferably, the drying temperature is 60 ℃.
A second object of the present invention is to provide a mesh-based MoSe 2 The Pt composite material modified electrode is prepared by adopting the method.
A third object of the present invention is to provide a non-enzymeHydrogen peroxide electrochemical sensor adopts three-electrode system, and working electrode adopts netlike MoSe 2 The Pt composite material modified electrode adopts a platinum wire as a counter electrode and adopts an Ag/AgCl electrode or a saturated calomel electrode as a reference electrode.
A fourth object of the present invention is to provide the mesh MoSe 2 The application of the Pt composite material modified electrode in hydrogen peroxide detection is as follows:
in the form of net of MoSe 2 The Pt composite material modified electrode is a working electrode, an Ag/AgCl or saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, electrolyte is liquid to be detected and buffer solution, the applied potential is 0 to-0.4V, and electrochemical measurement is carried out by adopting a cyclic voltammetry or a chronoamperometry.
The buffer solution is PBS solution prepared from disodium hydrogen phosphate, sodium dihydrogen phosphate and NaCl according to a certain proportion, and the pH value is 7.4.
Preferably, the modified electrode pretreatment will be based on reticulated MoSe 2 The Pt composite modified electrode was scanned for cyclic voltammograms in PBS buffer at ph=7.4 until a stable cyclic voltammogram was obtained.
The beneficial effects of the invention are as follows:
the invention uses net-shaped MoSe 2 As a conductive substrate, pt nano particles are used as electrode modification materials, and the prepared netlike MoSe 2 the/Pt composite material modified electrode can be applied to electrochemical enzyme-free detection of H 2 O 2 . The modified electrode has very high sensitivity and a large detection range (8-6818 mu M), and can rapidly realize H in a neutral medium in real time 2 O 2 Is detected.
The preparation process of the invention does not involve complex mechanism, has strong universality, the synthesis method is safe and stable, the prepared product is of nanometer level, and the sample is uniformly distributed. The invention uses net-shaped MoSe 2 Is a conductive substrate, on the one hand, a network of MoSe 2 Preventing agglomeration of Pt nanoparticles to improve conductivity; on the other hand, net-like MoSe having a porous structure 2 Synergistic effect with noble metal Pt, and size effect of noble metal Pt can improve conductivity and catalysisThe chemical efficiency is favorable for high-efficiency and sensitive electrochemical detection of hydrogen peroxide. The sensor constructed by the invention is an enzyme-free sensor, does not need harsh detection conditions, has good stability and repeatability, and is easy to be practically applied.
Drawings
FIG. 1 is a network MoSe of example 1 2 Is a transmission electron microscope photograph of (2).
FIG. 2 is a network MoSe of example 1 2 Transmission electron microscope photograph of the Pt composite.
FIG. 3 is a network MoSe of example 1 2 And net-shaped MoSe 2 XRD pattern of Pt composite material.
FIG. 4 is a network MoSe of example 2 2 Comparison of cyclic voltammograms of Pt composite modified electrodes with and without hydrogen peroxide.
FIGS. 5 (a) - (b) are, respectively, mesh MoSe of example 2 2 Response current and hydrogen peroxide addition standard curve of the Pt composite material modified electrode.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have long studied and practiced in a large number of ways, and have proposed the technical solution of the present invention, which is based on at least:
the net-shaped MoSe of the invention 2 Has a similar structure to molybdenum disulfide (MoS 2 ) The porous network of the sandwich layered structure exposes more defects and edges, providing more active sites capable of modifying noble metal nanoparticles, thereby more facilitating the dispersion and performance enhancement of noble metals. The invention uses net-shaped MoSe 2 Is a conductive substrate, on the one hand, a network of MoSe 2 Preventing agglomeration of Pt nanoparticles to improve conductivity; moSe after noble metal modification 2 And the synergistic effect of the noble metal and the size effect of the noble metal can improve the conductivity and catalytic efficiency.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In a first aspect, a mesh-based MoSe is provided 2 The preparation method of the Pt composite material modified electrode comprises the following steps:
step (1): preparation of reticulated MoSe by hard template method 2
1-1 preparation of KIT-6 as template:
dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 in a mixed solution of hydrochloric acid and deionized water with a certain concentration, uniformly stirring, adding n-BuOH, vigorously stirring, and finally adding TEOS to obtain a mixture; and carrying out hydrothermal treatment on the mixture, collecting white solid, and removing the surfactant through calcination to obtain the KIT-6 template.
1-2 KIT-6 template was reacted with PMA (H 3 PMo 12 O 40 6H 2 O) stirring and mixing in ethanol at room temperature, and obtaining PMA@KIT-6 composite powder after ethanol is completely evaporated;
1-3 mixing the PMA@KIT-6 composite powder with selenium powder, transferring the mixture into a quartz boat, calcining under a hydrogen stream, and finally removing the silica template by using an HF solution.
Step (2): net-shaped MoSe 2 Preparation of Pt composite material:
weighing PtCl with a certain proportion 4 And net-shaped MoSe 2 Adding hydrochloric acid, performing ultrasonic treatment, stirring at a certain temperature until drying, transferring the solid into a hydrogen furnace, calcining, taking out, and crushing to obtain netlike MoSe 2 Pt composite. The PtCl 4 And net-shaped MoSe 2 The molar ratio of (2) is 0.25-1:1.
preferably, the PtCl 4 And net-shaped MoSe 2 The molar ratio of (2) is 1:1.
step (3): preparation of catalyst ink:
the prepared net-shaped MoSe 2 Mixing the Pt composite material with ethanol and perfluorinated sulfonic acid resin Nafion, and performing ultrasonic treatment for more than 1h to prepare catalyst ink with the concentration of 0.01-0.1 g/ml;
preferably, the volume ratio of the perfluorinated sulfonic acid resin Nafion to the ethanol is 0.5-1.5:100.
step (4): polishing and cleaning the glassy carbon electrode;
preferably, in the step (4), a proper amount of alumina powder with the diameter of 0.3 mu m and 0.05 mu m is placed on polishing cloth, a small amount of water is added, the electrodes are sequentially polished into mirror surfaces, the glassy carbon electrodes are respectively immersed into deionized water, ethanol and deionized water for ultrasonic cleaning for 1-2 min, and then the glassy carbon electrodes are immersed in H 2 SO 4 Scanning the solution by cyclic voltammetry until a stable cyclic voltammetry curve is obtained, taking out, washing with deionized water, and using N 2 And drying for standby.
Step (5): preparation of modified electrode:
dropping the catalyst ink prepared in the step (3) on the surface of the glassy carbon electrode treated in the step (4), and drying in an oven; wherein the drop amount of the catalyst ink is 3-9 mu L.
Preferably, the drying temperature is 60 ℃.
Step (6): pretreatment of the modified electrode:
and (3) carrying out cyclic voltammetry scanning on the modified electrode prepared in the step (5) in PBS buffer solution with pH=7.4 until a stable cyclic voltammetry curve is obtained.
In a second aspect, a mesh-based MoSe is provided 2 The Pt composite material modified electrode is prepared by adopting the method.
In a third aspect, a non-enzymatic hydrogen peroxide electrochemical sensor is provided, employing a three-electrode system, the working electrode employing reticulated MoSe 2 The Pt composite material modified electrode adopts a platinum wire as a counter electrode and adopts an Ag/AgCl electrode or a saturated calomel electrode as a reference electrode.
In a fourth aspect, there is provided the reticulated MoSe 2 The application of the Pt composite material modified electrode in hydrogen peroxide detection is as follows:
in the form of net of MoSe 2 The Pt composite material modified electrode is used as a working electrode, an Ag/AgCl or saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, electrolyte is liquid to be detected and buffer solution, the applied potential is 0 to-0.4V, and electrochemical measurement is carried out by adopting a cyclic voltammetry or a chronoamperometry。
In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other. The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1:
20g of P123 were dissolved in 33ml of a mixed solution of 37% hydrochloric acid and 720ml of deionized water with stirring at 35℃and then 20g of n-BuOH were poured into the solution, stirred vigorously for 60min, and after 43g of TEOS had been added, stirred for 24h. Transferring the obtained mixture into a hydrothermal kettle, performing hydrothermal treatment at 100 ℃ for 24 hours, collecting white solid, and calcining in air at 550 ℃ for 6 hours at a heating rate of 1.5 ℃/min to remove the surfactant, thus obtaining the KIT-6. 0.5g KIT-6 was reacted with 0.8g PMA (H 3 PMo 12 O 40 6H 2 O) in 20ml of ethanol at room temperature. After complete evaporation of the ethanol, the PMA@KIT-6 composite powder was mixed with 1.3g of selenium powder. The mixture was then transferred to a quartz boat and rapidly warmed to 600 ℃ in a preheated tube furnace under a stream of hydrogen (200 ml/min), held for 4h, the product was removed and cooled to room temperature. Finally, the silica template was removed with 10% hf solution.
0.863g PtCl was weighed in a 5mL beaker 4 And 0.5g of the prepared reticulated MoSe 2 Adding 10mL of 12M hydrochloric acid, ultrasonic stirring for 5min at 80deg.C in water bath at 200rpm until dry, transferring the solid into quartz boat while hot, placing the quartz boat in the middle of quartz tube, preheating the tube furnace to 350deg.C, placing the quartz tube into the tube furnace, reacting under hydrogen for 1 hr, taking out, and crushing to obtain netlike MoSe 2 Pt composite.
Weighing 4mg of the prepared netlike MoSe 2 The Pt composite material and 400 mu l of ethanol and 100 mu l of Nafion ethanol solution with the volume content of 5% are prepared into catalyst ink, and the catalyst ink is subjected to ultrasonic treatment for 1h to obtain the uniformly dispersed catalyst ink.
Proper amount of alumina powder of 0.3 μm and 0.05 μm is put into polishingAdding a small amount of water on the cloth, sequentially polishing the electrodes into mirror surfaces, respectively immersing the electrodes in deionized water, ethanol and deionized water, ultrasonically cleaning for 1-2 min, and immersing the glassy carbon electrode in 0.5. 0.5M H 2 SO 4 Scanning the solution by cyclic voltammetry until a stable cyclic voltammetry curve is obtained, taking out, washing with deionized water, and using N 2 And drying for standby.
The prepared catalyst ink was applied dropwise to the surface of the glassy carbon electrode, dried in an oven at 60℃in an amount of 6. Mu.l, and was added dropwise in two portions.
To obtain net-shaped MoSe 2 And (3) taking the glassy carbon electrode modified by the Pt composite material as a working electrode, taking a platinum wire as a counter electrode, taking an Ag/AgCl electrode as a reference electrode, and preparing the electrochemical sensor by using the working electrode, the counter electrode and the reference electrode.
And (3) carrying out pretreatment on the modified electrode before electrochemical detection of hydrogen peroxide, and carrying out cyclic voltammetry scanning on the prepared modified electrode in PBS buffer solution with pH=7.4, wherein the scanning potential range is-0.3-0.6V until a stable cyclic voltammetry curve is obtained.
As shown in FIGS. 1-2, the reticulated MoSe of example 1 was examined under a transmission electron microscope 2 And net-shaped MoSe 2 Observation of the Pt composite material shows that the netlike MoSe 2 The whole body is in a porous net structure, and the net MoSe is formed 2 In the Pt composite material, pt is uniformly dispersed in the netlike MoSe 2 The two materials are tightly combined, pt is in net MoSe 2 The surface dispersibility is good, and the agglomeration phenomenon is avoided.
As shown in FIG. 3, the network MoSe of example 1 was characterized by X-ray diffraction (XRD) 2 Characterization of the Pt composite material, it was found that the composite material was composed of MoSe 2 And typical peak composition of Pt.
The electrochemical sensor prepared according to example 1 was used for the detection of hydrogen peroxide.
The test method was an electrochemical test using an electrochemical workstation with a 0.1M PBS solution (ph=7.4) as electrolyte, and the detection potential was 0V (Ag/AgCl electrode). The electrochemical response of hydrogen peroxide was tested by adding hydrogen peroxide at different concentrations using a time-current curve test.
Reticulated MoSe prepared by cyclic voltammogram pairs at different hydrogen peroxide concentrations 2 The glass carbon electrode modified by the Pt composite material has good electrochemical response capability to hydrogen peroxide.
Electrochemical detection of hydrogen peroxide is performed by means of time-current curves at different concentrations, wherein the response current versus hydrogen peroxide concentration can be well verified by means of a drawn standard curve.
Example 2:
20g of P123 were dissolved in 33ml of a mixed solution of 37% hydrochloric acid and 720ml of deionized water with stirring at 35℃and then 20g of n-BuOH were poured into the solution, stirred vigorously for 60min, and after 43g of TEOS had been added, stirred for 24h. Transferring the obtained mixture into a hydrothermal kettle, performing hydrothermal treatment at 100deg.C for 24 hr, collecting white solid, and standing in air at 1.5deg.C for min -1 Calcining at 550 ℃ for 6 hours to remove the surfactant, thus obtaining the KIT-6. 0.5g KIT-6 was reacted with 0.8g PMA (H 3 PMo 12 O 40 6H 2 O) in 20ml of ethanol at room temperature. After complete evaporation of the ethanol, the PMA@KIT-6 composite powder was mixed with 1.3g of selenium powder. The mixture was then transferred to a quartz boat and rapidly warmed to 600 ℃ in a preheated tube furnace under a stream of hydrogen (200 ml/min), held for 4h, the product was removed and cooled to room temperature. Finally, the silica template was removed with 10% hf solution.
0.863g PtCl was weighed in a 5mL beaker 4 And 0.5g of the reticulated MoSe prepared in step (1) 2 Adding 10mL of 12M hydrochloric acid, ultrasonic stirring for 5min at 80deg.C in water bath at 200rpm until dry, transferring the solid into quartz boat while hot, placing the quartz boat in the middle of quartz tube, preheating the tube furnace to 350deg.C, placing the quartz tube into the tube furnace, reacting under hydrogen for 1 hr, taking out, and crushing to obtain netlike MoSe 2 Pt composite.
Weighing 4mg of the netlike MoSe prepared in the step (2) 2 Preparing catalyst ink by the Pt composite material and 400 mu l of ethanol and 50 mu l of Nafion ethanol solution with the volume content of 5%, and carrying out ultrasonic treatment for 2 hours to obtain the uniformly dispersed catalyst ink。
Placing proper amount of 0.3 μm and 0.05 μm alumina powder on polishing cloth, adding small amount of water, sequentially polishing the electrodes to mirror surface, respectively soaking the electrodes in deionized water, ethanol and deionized water, ultrasonically cleaning for 5min, and soaking the glassy carbon electrode in 0.5M H 2 SO 4 Scanning the solution by cyclic voltammetry until a stable cyclic voltammetry curve is obtained, taking out, washing with deionized water, and using N 2 And drying for standby.
The prepared catalyst ink was applied dropwise to the surface of the glassy carbon electrode, dried in an oven at 60℃in an amount of 7. Mu.l, and was added dropwise in two portions.
To obtain net-shaped MoSe 2 And (3) taking the glassy carbon electrode modified by the Pt composite material as a working electrode, taking a platinum wire as a counter electrode, taking an Ag/AgCl electrode as a reference electrode, and preparing the electrochemical sensor by using the working electrode, the counter electrode and the reference electrode.
And (3) carrying out pretreatment on the modified electrode before electrochemical detection of hydrogen peroxide, and carrying out cyclic voltammetry scanning on the prepared modified electrode in PBS buffer solution with pH=7.4, wherein the scanning potential range is-0.6-0.6V until a stable cyclic voltammetry curve is obtained.
The reticulated MoSe of example 1 was examined under a transmission electron microscope 2 And net-shaped MoSe 2 Observation of the Pt composite material shows that the netlike MoSe 2 The whole body is in a porous net structure, and the net MoSe is formed 2 In the Pt composite material, pt is uniformly dispersed in the netlike MoSe 2 The two materials are tightly combined, pt is in net MoSe 2 The surface dispersibility is good, and the agglomeration phenomenon is avoided.
The network MoSe of example 1 was characterized by X-ray diffraction 2 Characterization of the Pt composite material, it was found that the composite material was composed of MoSe 2 And Pt, demonstrating successful composite preparation.
The electrochemical sensor prepared according to example 2 was used for the detection of hydrogen peroxide.
The test method was an electrochemical test using an electrochemical workstation with a 0.1M PBS solution (ph=7.4) as electrolyte, and the detection potential was 0V (Ag/AgCl electrode). The electrochemical response of hydrogen peroxide was tested by adding hydrogen peroxide at different concentrations using a time-current curve test.
As shown in FIG. 4, the MoSe net was treated with hydrogen peroxide at 1.0mM and without hydrogen peroxide 2 Comparing the cyclic voltammograms of the Pt composite material modified glassy carbon electrode can show that the prepared netlike MoSe 2 The glass carbon electrode modified by the Pt composite material has good electrochemical response capability to hydrogen peroxide.
Electrochemical detection of hydrogen peroxide by time-current curves at different concentrations as shown in FIG. 5, wherein the response current versus hydrogen peroxide concentration relationship can be well verified by the plotted standard curve, showing good linear relationship (R 2 =0.9997), the standard curve of which is y= -0.0105x-6.98.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (9)
1. MoSe based on net shape 2 The preparation method of the Pt composite material modified electrode is characterized by comprising the following steps of:
step (1): preparation of reticulated MoSe by hard template method 2 ：
1-1 preparation of KIT-6 as template:
dissolving a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 in a mixed solution of hydrochloric acid and deionized water with a certain concentration, uniformly stirring, adding n-BuOH, vigorously stirring, and finally adding TEOS to obtain a mixture; carrying out hydrothermal treatment on the mixture, collecting white solid, and removing a surfactant through calcination to obtain a KIT-6 template;
1-2 stirring and mixing the KIT-6 template and PMA in ethanol at room temperature, and obtaining PMA@KIT-6 composite powder after ethanol is completely evaporated;
1-3, mixing PMA@KIT-6 composite powder with selenium powder, transferring the mixture into a quartz boat, calcining under a hydrogen flow, and finally removing a silicon dioxide template by using an HF solution;
step (2): net-shaped MoSe 2 Preparation of Pt composite material:
weighing PtCl with a certain proportion 4 And net-shaped MoSe 2 Adding hydrochloric acid, performing ultrasonic treatment, stirring at a certain temperature until drying, transferring the solid into a hydrogen furnace, calcining, taking out, and crushing to obtain netlike MoSe 2 a/Pt composite material; the PtCl 4 And net-shaped MoSe 2 The molar ratio of (2) is 0.25-1:1, a step of;
step (3): preparation of catalyst ink:
the prepared net-shaped MoSe 2 Mixing the Pt composite material with ethanol and perfluorinated sulfonic acid resin Nafion, and performing ultrasonic treatment for more than 1h to prepare catalyst ink with the concentration of 0.01-0.1 g/ml;
step (4): polishing and cleaning the glassy carbon electrode;
step (5): dropping the catalyst ink prepared in the step (3) on the surface of the glassy carbon electrode treated in the step (4), and drying in an oven to obtain the netlike MoSe-based catalyst ink 2 The Pt composite material modifies the electrode; wherein the drop amount of the catalyst ink is 3-9 mu L.
2. The method according to claim 1, characterized in that the PtCl of step (2) 4 And net-shaped MoSe 2 The molar ratio of (2) is 1:1.
3. the method according to claim 1, wherein the volume ratio of Nafion to ethanol of the perfluorosulfonic acid resin in step (3) is 0.5 to 1.5:100.
4. MoSe based on net shape 2 A Pt composite modified electrode prepared by the method of any one of claims 1-3.
5. A non-enzymatic hydrogen peroxide electrochemical sensor adopts a three-electrode system, a counter electrode adopts a platinum wire, a reference electrode adopts an Ag/AgCl electrode or a saturated calomel electrode, and is characterized in that a working electrode adopts the netlike MoSe-based electrode according to claim 4 2 The Pt composite material modifies the electrode.
6. A mesh-based MoSe as recited in claim 4 2 Application of Pt composite material modified electrode in hydrogen peroxide detection.
7. Use according to claim 6, characterized in that it is in particular:
a mesh-based MoSe as recited in claim 4 2 The Pt composite material modified electrode is a working electrode, an Ag/AgCl or saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, electrolyte is liquid to be detected and buffer solution, the applied potential is 0 to-0.4V, and electrochemical measurement is carried out by adopting a cyclic voltammetry or a chronoamperometry.
8. The method according to claim 7, wherein the buffer solution is prepared from disodium hydrogen phosphate, sodium dihydrogen phosphate and NaCl according to a certain proportion, and the pH value is 7.4.
9. The use according to claim 7, characterized in that it is based on mesh MoSe 2 The pretreatment of the Pt composite material modified electrode is based on net-shaped MoSe 2 The Pt composite modified electrode was scanned for cyclic voltammograms in PBS buffer at ph=7.4 until a stable cyclic voltammogram was obtained.
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| CN108593743A (en) * | 2018-05-09 | 2018-09-28 | 山东理工大学 | A kind of preparation method and application of the interlayer type immunosensor of the compound two selenizings molybdenum label of platinum palladium |
| CN113798491A (en) * | 2021-09-17 | 2021-12-17 | 杭州师范大学 | Dumbbell-shaped copper-containing composite precious metal nano material and synthesis method thereof |
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| CN108593743A (en) * | 2018-05-09 | 2018-09-28 | 山东理工大学 | A kind of preparation method and application of the interlayer type immunosensor of the compound two selenizings molybdenum label of platinum palladium |
| CN113798491A (en) * | 2021-09-17 | 2021-12-17 | 杭州师范大学 | Dumbbell-shaped copper-containing composite precious metal nano material and synthesis method thereof |
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| Facile construction of an Ag/MoSe2 composite based non-enzymatic amperometric sensor for hydrogen peroxide;Ran Tian等;《Dalton Trans》;第51卷;第5271-5277页 * |
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