CN113376234A - Cu-based flexible non-enzymatic lactate sensor electrode membrane and preparation method thereof - Google Patents
Cu-based flexible non-enzymatic lactate sensor electrode membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a Cu-based flexible non-enzymatic lactate sensor electrode film and a preparation method thereof. The preparation method adopts a BC membrane as a carrier for constructing a flexible electrode material in a biosensor, uses a multi-walled carbon nano tube with good conductivity and large specific surface area as a conductive material, firstly, the BC/c-MWCNTs nano composite membrane is prepared by compounding the BC membrane and the conductive multi-walled carbon nano tube, and in order to regulate and control the morphology and the size of MOFs, pyrrole is polymerized on the BC/c-MWCNTs nano composite membrane by an electrochemical polymerization method to obtain the BC/c-MWCNTs/PPy nano composite membrane; in order to further improve the detection sensitivity of the lactic acid, Cu-MOFs is deposited on the surface of the conductive BC/c-MWCNTs/PPy nano composite membrane by an electrochemical deposition method, and the electrode membrane of the Cu-based flexible non-enzymatic lactic acid sensor is prepared. The electrode film has the advantages of good stability, low cost and long service life when detecting lactic acid, is not influenced by environment, temperature, pH and the like, is easy to store, can effectively reflect the concentration of the lactic acid in human sweat in real time through the detection of the electrode film, judges whether the movement is excessive, and has huge application prospect.
Description
Technical Field
The invention relates to the technical field of flexible electrode film preparation, in particular to a Cu-based flexible non-enzymatic lactic acid sensor electrode film and a preparation method thereof.
Background
At present, the general lactic acid detector in the market mainly adopts an invasive sensor to collect blood of capillary vessels of fingertips of a testee in a needle inserting mode, repeated collection has great harm, real-time detection cannot be realized, and the lactic acid detector is not easy to popularize.
Related reports in the prior art relate to a sensor electrode for detecting the content of lactic acid in human sweat and saliva, which is mainly prepared by using lactate oxidase. For example, the invention patent with application number CN202011132178.3 discloses a preparation method of a lactate biosensor. The sensor is based on an electrochemical deposition method, copper and iron are electrodeposited on a certain amount of copper nanowires in situ, and the growth of the nano material is regulated and controlled by adjusting the electrodeposition method and the electrodeposition conditions, so that the catalytic activity and the conductivity of the material are regulated and controlled. However, this lactate enzyme sensor has the following drawbacks: lactate oxidase is difficult to extract and expensive, and the activity of the lactate oxidase is obviously influenced by environmental factors such as temperature, oxygen concentration, pH value, humidity and the like, for example, the lactate oxidase is obviously inactivated under the room temperature condition, so that the stability, sensitivity and reproducibility of the lactate sensor are influenced, and the storage and use conditions of the lactate sensor are harsh.
The non-enzymatic lactate sensing electrode can basically solve the defects of an enzymatic lactate sensor and has the advantages of quick response, wide detection limit, good stability, simple preparation, low cost and the like.
The invention patent with the application number of CN201810770970.8 discloses a carbon nano tube/polypyrrole composite fiber, a preparation method and application thereof in a transistor sensor. The preparation method comprises the steps of coating the dispersed carbon nano tubes on the flexible fibers, and then chemically polymerizing pyrrole monomers on the flexible fibers containing the coated carbon nano tubes in situ. However, the method has the defects of narrow detection range and incapability of being directly used for monitoring the concentration of the sweat lactic acid.
In view of the above, there is a need to design an improved flexible non-enzymatic lactate sensor electrode film for detecting the lactate content in human sweat with accuracy and little environmental impact, and a method for manufacturing the same, so as to solve the above problems.
Disclosure of Invention
The invention aims to provide a Cu-based flexible non-enzymatic lactate sensor electrode film and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor, comprising the steps of:
s1, preparing a conductive BC/c-MWCNTs nano composite membrane: preparing a c-MWCNTs suspension with a preset concentration; pretreating the BC membrane, then soaking the pretreated BC membrane in the c-MWCNTs suspension for ultrasonic treatment for 4-6 h, taking out and cleaning to prepare a conductive BC/c-MWCNTs nano composite membrane;
s2, preparing a BC/c-MWCNTs/PPy nano composite membrane: preparing pyrrole monomer solution; clamping the conductive BC/c-MWCNTs nano composite membrane by using an electrode clamp to serve as a working electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking the pyrrole monomer solution as an electrolyte to perform electrochemical polymerization reaction, and after the polymerization is finished, performing vacuum drying treatment at the temperature of 60-80 ℃ to obtain the BC/c-MWCNTs/PPy nano composite membrane;
s3, preparing an electrode film of the Cu-based flexible non-enzymatic lactate sensor: preparing a copper plating solution; clamping the BC/c-MWCNTs/PPy nano composite membrane by using an electrode clamp to serve as a working electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, and taking the copper plating solution as an electrolyte to perform electrochemical deposition reaction, so as to generate a layer of Cu-MOFs on the BC/c-MWCNTs/PPy nano composite membrane; and then drying the film after the deposition reaction to prepare the Cu-based flexible non-enzymatic lactate sensor electrode film.
As a further improvement of the present invention, in step S2, the preparation process of the pyrrole monomer solution is as follows: dissolving 0.05-0.09M lithium perchlorate and 0.01-0.03 wt% soluble starch in 0.05-0.2M phosphate buffer solution, stirring for 15-45 min, adding 0.14-0.28M pyrrole into the mixed solution, and completely mixing to obtain a pyrrole prepolymer solution.
As a further improvement of the present invention, in step S2, the process of electrochemical polymerization is set as follows: an electrochemical workstation is used as a reaction device, a constant voltage method is adopted, the reaction potential is set to be 0.6-1.0V, and the reaction time is set to be 120-180 s.
As a further improvement of the present invention, in step S3, the preparation process of the copper plating solution is: dissolving 1, 3, 5-benzene tricarbonic acid in N, N-dimethylformamide to obtain a solution A; dissolving triethylamine hydrochloride and copper sulfate trihydrate with a predetermined ratio in water to obtain a solution B; and uniformly mixing the solution A and the solution B to prepare the copper plating solution.
As a further improvement of the invention, in the copper plating solution, the molar ratio of 1, 3, 5-benzene tricarboxylic acid, triethylamine hydrochloride and copper sulfate trihydrate is (0.0005-0.002): (0.0001-0.0003): (0.01-0.03).
As a further improvement of the present invention, in step S3, the process of electrochemical deposition is set as follows: an electrochemical workstation is used as a reaction device, a constant voltage method is adopted, the reaction potential is set to be-0.3 to-0.7 v, and the reaction time is set to be 5 to 15 min.
As a further improvement of the invention, in step S1, the preparation process of the c-MWCNTs suspension is as follows: firstly, preparing a uniform suspension of c-MWCNTs with the concentration of 0.5-2 mg/mL, adding a predetermined amount of hexadecyl ammonium bromide, and performing ultrasonic dispersion for 4-6 hours under an ultrasonic process with the power of 200-400W and the frequency of 30-50 kHz to obtain the suspension of the c-MWCNTs.
As a further improvement of the present invention, in step S1, the pretreatment process of the BC membrane is: soaking the BC membrane in a solution with the concentration of 0.5-2.0 mol.L-1Treating in NaOH solution at a constant temperature of 70-90 ℃ for 1-3 h in a constant-temperature water bath, taking out the treated BC membrane, and rinsing the BC membrane to be neutral by using clear water; next, the cleaned BC film was cut into a predetermined size.
In order to realize the purpose, the invention also provides a Cu-based flexible non-enzymatic lactate sensor electrode membrane prepared by the preparation method, which is prepared by compounding a BC membrane serving as a flexible carrier and c-MWCNTs serving as a conductive material to prepare a conductive BC/c-MWCNTs nano composite membrane, and then sequentially carrying out pyrrole polymerization and Cu-MoFs deposition construction on the conductive BC/c-MWCNTs nano composite membrane by an electrochemical deposition method.
In order to realize the aim of the invention, the detection range of the electrode film of the Cu-based flexible non-enzymatic lactate sensor is 0.5-20mM of lactate concentration.
The invention has the beneficial effects that:
1. the invention provides a preparation method of a Cu-based flexible non-enzymatic lactate sensor electrode membrane, which uses a BC membrane as a carrier for constructing a flexible electrode material in a biosensor, uses a multi-walled carbon nano tube with good conductivity and large specific surface area as a conductive material to prepare a conductive BC/c-MWCNTs nano composite membrane, and uses an electrochemical deposition method to polymerize pyrrole on the BC/c-MWCNTs nano composite membrane in order to regulate the shape and size of MOFs, and simultaneously uses an electrochemical deposition method to deposit Cu-MOFs on the surface of the conductive BC/c-MWCNTs/PPy nano composite membrane in order to further improve the detection sensitivity of lactate so as to prepare the Cu-based flexible non-enzymatic lactate sensor electrode membrane, which has the advantages of high detection sensitivity, accurate detection result, small environmental influence, wider detection range and excellent detection stability, the mechanism is as follows:
1) when the BC membrane is used as an electrode carrier of the lactic acid sensor, sweat can be well absorbed, and the detection sensitivity is improved; meanwhile, based on the characteristics of a BC controllable growth environment, a three-dimensional nano-mesh structure, a large specific surface area, high flexibility, rich functional groups and the like, an excellent microenvironment and active sites are provided for immobilization of the functional nano-material, the BC-based nano-composite material with controllable morphology can be constructed, and interface performance regulation of the BC material is further realized through surface functionalization. In addition, the BC film has good tear resistance, shape maintaining capacity and directly degradable environmental protection performance.
2) The conductive multi-wall carbon nano tube has high surface activity and is easy to generate electron transfer with other substances, thereby accelerating the electron transfer rate of a heterogeneous interface and promoting the electron transfer, and the conductive multi-wall carbon nano tube is an excellent electrode modification material. And the multi-walled carbon nano-tube can be adsorbed on the BC film by utilizing the hydrogen bond function and used as a template to induce the growth of the subsequent MOFs, thereby further controlling the appearance of the multi-walled carbon nano-tube.
3) By utilizing a two-step electrochemical deposition combined process, polypyrrole and Cu-MOFs are sequentially deposited on the surface of the BC/c-MWCNTs nano composite membrane, and structural regulation molecules such as the polypyrrole can realize oriented growth of the MOFs, and the morphology and the size of the MOFs are regulated by the polypyrrole, so that the lactic acid response capability of the MOFs is improved. Meanwhile, in the invention, the polypyrrole can be subjected to p-type doping with lactic acid anions, so that the conductivity of the polypyrrole can be improved, and therefore, the PPy and the MOFs have a synergistic effect, and the PPy-MOFs composite material not only has the advantage of large specific surface area of the MOFs, but also can play a role in the rapid electron transfer capability of the PPy. The doping of MOFs in PPY can also improve the performance of PPY, improve the stability of PPy in the electrochemical cycle process and improve the mechanical property and the electrochemical property of the composite material. The detection range of the lactic acid can be widened and the detection stability can be improved.
4) The MOFs have the advantages of flexibly adjustable pore size, extremely high porosity, large specific surface area, easily modified chemical property, easily modified structural diversity and the like, and have great development prospect and application potential due to the unique advantages of good stability and repeatability in the preparation of non-enzymatic sensors. In the invention, the electrochemical property of the Cu-MOFs depends on the used organic ligand, and the Cu-MOFs synthesized by DMF has good electrochemical performance. Meanwhile, the active site density of the Cu-BTC is high, and good electrochemical activity can be provided. And the copper is used as a catalytic center, so that the sensitization effect on the lactic acid test is obvious, and the repeatability and the stability of the electrode are good.
5) The copper plating solution is a mixed solution of a 1, 3, 5-benzene trimethyl acid solution and a copper sulfate trihydrate solution, so that the cost is low, the synthesis is easy, and the copper plating solution can be well and uniformly mixed; and the damage of the pure solution to the BC membrane can be effectively reduced, and the BC membrane is prevented from being corroded. Meanwhile, the electrochemical deposition method is used, so that the reaction is quicker and the adhesion is firmer. Meanwhile, the adopted electrochemical polymerization method is simple to operate, the conditions are easy to control, the conductive performance and the mechanical property of the synthesized conductive high molecular polymer are excellent, and the longer the polymerization time is, the more the polymerization amount is under the same potential. The electrochemical synthesis method is easier to prepare the MOFs film, has high reaction speed and can synthesize the film within dozens of minutes or hours; the reaction condition is mild, and the reaction can be carried out at room temperature, so that the energy consumption is saved; the synthetic raw materials can be fully utilized in the synthetic process, so that the loss is little, and the continuous production is convenient to realize; the synthesis conditions are easy to control, and the experimental equipment is simple.
2. The Cu-based flexible non-enzymatic lactate sensor electrode film provided by the invention has the advantages of good stability, low cost, long service life, no influence of environment, temperature, pH and the like when detecting lactate, and easy storage. Through detection, the concentration of lactic acid in human sweat can be effectively reflected in real time, and whether the movement is excessive or not is judged, particularly in the process of monitoring and treating patients with hypoxia caused by various diseases and testing physical ability of athletes. The detection range of the electrode membrane of the Cu-based flexible non-enzymatic lactate sensor is 0.5-20mM of lactate concentration.
Drawings
FIG. 1 is a flow chart of experimental preparation provided by the present invention.
Fig. 2 is a response curve of lactate titration performed by the electrode film of the Cu-based flexible non-enzymatic lactate sensor provided in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the present invention provides a method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor, comprising the following steps:
s1, preparing a conductive BC/c-MWCNTs nano composite membrane: preparing a c-MWCNTs suspension with a preset concentration; pretreating the BC membrane, then soaking the pretreated BC membrane in the c-MWCNTs suspension for ultrasonic treatment for 4-6 h, taking out and cleaning to prepare a conductive BC/c-MWCNTs nano composite membrane;
s2, preparing a BC/c-MWCNTs/PPy nano composite membrane: preparing pyrrole monomer solution; clamping the conductive BC/c-MWCNTs nano composite membrane by using an electrode clamp to serve as a working electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking the pyrrole monomer solution as an electrolyte to perform electrochemical polymerization reaction, and after the polymerization is finished, performing vacuum drying treatment at the temperature of 60-80 ℃ to obtain the BC/c-MWCNTs/PPy nano composite membrane;
s3, preparing an electrode film of the Cu-based flexible non-enzymatic lactate sensor: preparing a copper plating solution; clamping the BC/c-MWCNTs/PPy nano composite membrane by using an electrode clamp to serve as a working electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, and taking the copper plating solution as an electrolyte to perform electrochemical deposition reaction, so as to generate a layer of Cu-MOFs on the BC/c-MWCNTs/PPy nano composite membrane; and then drying the film after the deposition reaction to prepare the Cu-based flexible non-enzymatic lactate sensor electrode film.
Preferably, in step S2, the preparation process of the pyrrole monomer solution is as follows: dissolving 0.05-0.09M lithium perchlorate and 0.01-0.03 wt% soluble starch in 0.05-0.2M phosphate buffer solution, stirring for 15-45 min, adding 0.14-0.28M pyrrole into the mixed solution, and completely mixing to obtain a pyrrole monomer solution.
Preferably, in step S2, the electrochemical polymerization process is set as follows: an electrochemical workstation is used as a reaction device, a constant voltage method is adopted, the reaction potential is set to be 0.6-1.0V, and the reaction time is set to be 120-180 s.
Preferably, in step S3, the preparation process of the copper plating solution is: dissolving 1, 3, 5-benzene tricarbonic acid in N, N-dimethylformamide to obtain a solution A; dissolving triethylamine hydrochloride and copper sulfate trihydrate with a predetermined ratio in water to obtain a solution B; and uniformly mixing the solution A and the solution B to prepare the copper plating solution.
Preferably, in the copper plating solution, the molar ratio of 1, 3, 5-benzenetricarboxylic acid, triethylamine hydrochloride and copper sulfate trihydrate is (0.0005-0.002): (0.0001-0.0003): (0.01-0.03).
Preferably, in step S3, the electrochemical deposition process is set as follows: an electrochemical workstation is used as a reaction device, a constant voltage method is adopted, the reaction potential is set to be-0.3 to-0.7 v, and the reaction time is set to be 5 to 15 min.
Preferably, in step S1, the c-MWCNTs suspension is prepared by the following process: firstly, preparing a uniform suspension of c-MWCNTs with the concentration of 0.5-2 mg/mL, adding a predetermined amount of hexadecyl ammonium bromide, and performing ultrasonic dispersion for 4-6 hours under an ultrasonic process with the power of 200-400W and the frequency of 30-50 kHz to obtain the suspension of the c-MWCNTs.
Preferably, in step S1, the BC membrane pretreatment process includes: soaking the BC membrane in a solution with the concentration of 0.5-2.0 mol.L-1Treating in NaOH solution at a constant temperature of 70-90 ℃ for 1-3 h in a constant-temperature water bath, taking out the treated BC membrane, and rinsing the BC membrane to be neutral by using clear water; next, the cleaned BC film was cut into a predetermined size.
The present invention will be described in detail with reference to specific examples.
Example 1
The embodiment 1 of the invention provides a preparation method of an electrode film of a Cu-based flexible non-enzymatic lactate sensor, which comprises the following steps:
s1, preparing a conductive BC/c-MWCNTs nano composite membrane:
preparing 100mL of uniform suspension of c-MWCNTs (multi-walled carbon nanotubes) with the concentration of 1mg/mL, and adding a certain amount (9 multiplied by 10)-4mol·L-1) The cetyl ammonium bromide (CTAB) and the c-MWCNTs uniform suspension are mixed to improve the dispersibility of the suspension, and then the suspension is ultrasonically dispersed for 5 hours at room temperature by an ultrasonic cleaner with the power of 300W and the frequency of 40kHz to prepare the c-MWCNTs suspension.
Soaking BC membrane in the solution with the concentration of 1 mol.L-1Treating in a constant-temperature water bath kettle at 80 ℃ for 2 hours to remove nutrient components and viable bacteria, taking out the treated BC membrane, and rinsing with deionized water until the pH value is 7; and then, preparing the cleaned BC membrane into a rectangular sheet with the thickness of 1cm multiplied by 2cm, soaking the BC membrane in the prepared c-MWCNTs suspension for ultrasonic treatment for 5 hours, taking out the BC/c-MWCNTs composite membrane, washing the BC/c-MWCNTs composite membrane by water to remove the c-MWCNTs with the surface not firmly combined, and obtaining the conductive BC/c-MWCNTs nano composite membrane for later use.
S2, preparing a BC/c-MWCNTs/PPy nano composite membrane:
0.07M LiClO was dissolved in 0.1M pbs (phosphate buffer)4(lithium perchlorate) and 0.02 wt% of soluble starch, stirring for 30min, adding 0.2M pyrrole into the mixed solution, and preparing pyrrole monomer solution for later use after the pyrrole is completely mixed.
The prepared conductive BC/c-MWCNTs nano composite membrane is clamped by an electrode clamp to be used as a working electrode, a platinum sheet electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode to prepare a three-electrode system, and polypyrrole nano wires with dispersed structures and uniform thickness can be obtained by electrodepositing 150s on a multiwall carbon nano tube substrate on an electrochemical workstation by a constant voltage method at the potential of 0.85 v. And after the polymerization is finished, placing the polymer in a vacuum oven at 75 ℃ for drying for 60 minutes to obtain the BC/c-MWCNTs/PPy nano composite membrane.
S3, preparing an electrode film of the Cu-based flexible non-enzymatic lactate sensor:
50mL of copper plating solution is prepared, and the process is as follows: dissolving 0.001mol of BTC (1, 3, 5-benzenetricarboxylic acid) in 25mL of DMF (N, N-dimethylformamide) to obtain a solution A; 0.0002mol of triethylamine hydrochloride and 0.02mol of copper sulfate trihydrate were dissolved in 25mL of deionized water to obtain solution B. And uniformly mixing the prepared solution A and the prepared solution B to obtain a copper plating solution for later use.
Clamping the prepared BC/c-MWCNTs/PPy nano composite membrane by using an electrode clamp as a working electrode, using a platinum sheet electrode as a counter electrode and using a saturated calomel electrode as a reference electrode to prepare a three-electrode system, placing the three-electrode system in copper plating solution, adopting an electrochemical workstation, performing deposition reaction for 10min by using a constant voltage method at a potential of-0.5V, and generating a layer of Cu-MOFs on the BC/c-MWCNTs/PPy nano composite membrane. And (3) drying the reacted film in an oven at 80 ℃ for 30min to obtain a Cu-based flexible non-enzymatic lactate sensor electrode film, sealing and placing in a dryer for later use.
S4, simulation test:
the dried Cu-based flexible non-enzymatic lactate sensor electrode film is clamped by an electrode clamp to be used as a working electrode, a platinum sheet electrode is used as a counter electrode, an Agcl electrode is used as a reference electrode to prepare a three-electrode system, and lactate titration is carried out in simulated sweat at a working potential of-0.2 v on an electrochemical workstation by a constant voltage method.
The lactic acid titration process is as follows: the dropwise addition of 80mM lactic acid solution was performed to 30ml of test solution (simulated sweat) at intervals of 50-100 s, and a response curve was generated on an electrochemical workstation, as shown in FIG. 2.
Fig. 2 shows that the electrode film of the Cu-based flexible non-enzymatic lactate sensor prepared in example 1 has excellent detection sensitivity, a wide detection range, and detection stability. As can be seen from FIG. 2, the response current value increased linearly with the increase in lactate concentration, and remained well linear at high concentration, indicating a wide detection range. Can carry out a good detection on the concentration of lactic acid in human sweat.
Fig. 1 shows the experimental preparation process and microstructure of the experimental electrode film.
Examples 2 to 6
The difference from the embodiment 1 of the present invention is that: the process parameter settings in step S2 and step S3 are different, as shown in the following table.
Examples 1 to 7 were analyzed in conjunction with table 1:
1) the influence of the process setting of electrochemical polymerization on the detection range of the prepared electrode film of the Cu-based flexible non-enzymatic lactate sensor is as follows: electrochemical polymerization reactions are, for the most part, carried out over a range of voltages, the magnitude of which determines the extent and rate at which electrochemical deposition reactions occur. The higher the voltage, the faster the polymerization reaction, and the denser the resultant polymerized layer, but the higher the voltage, the transmission between polymer particles is hindered, and the subsequent reaction is affected.
When polymerizing pyrrole, the polymerization amount increases with the increase of polymerization time when the polymerization voltage is the same, but when the polymerization time is too long, the polymerization layer becomes too thick due to the excessive polymerization amount, resulting in the deterioration of its properties. In the experiment, it is found that when the polymerization time is 150s, a complete polymerization layer can be formed, the performance is excellent, and the polymerization layer becomes thick when the time is prolonged.
The thickness of the deposited PPy film is greatly influenced by the pyrrole concentration, and under the same other conditions, the higher the salt content in the solution, the easier the electrochemical reaction proceeds, the larger the amount of the generated product, and the pyrrole concentration also influences the surface morphology, structure and properties of the deposited layer. The PPy film prepared by higher pyrrole concentration has uneven small particles, which causes uneven and rough surface of the formed film.
2) The influence of the process setting of electrochemical deposition on the detection range of the prepared electrode film of the Cu-based flexible non-enzymatic lactate sensor is as follows: it is known that in the process of electrochemically preparing MOFs, the precursor solution (such as species, concentration, PH value) and electrodeposition parameters (such as voltage, deposition time) used for synthesizing MOFs determine the structure, surface morphology and properties of the synthesized MOFs.
Cu-BTC films prepared at different voltages have the same composition, but differ in morphology, electrochemical activity and electron transfer capability.
The microstructure shows that the Cu-BTC film is formed by stacking nano sheets with different sizes layer by layer, the size of the nano sheets is larger when the deposition voltage (absolute value) is smaller, and the size of the nano sheets is gradually reduced when the absolute value of the deposition voltage (negative voltage) is gradually increased, but some gaps can be seen in the stacked layered structure. The decrease in the nanometer size with increasing absolute value of voltage is probably due to the increased nucleation rate at more negative voltages and the faster synthesis of Cu-BTC films, but the increased film thickness and the decreased electrochemical activity and electron transfer capability.
In conclusion, the invention provides a Cu-based flexible non-enzymatic lactate sensor electrode film and a preparation method thereof. The preparation method adopts a BC membrane as a carrier for constructing a flexible electrode material in a biosensor, uses a multi-walled carbon nano tube with good conductivity and large specific surface area as a conductive material, firstly, the BC/c-MWCNTs nano composite membrane is prepared by compounding the BC membrane and the conductive multi-walled carbon nano tube, and in order to regulate and control the morphology and the size of MOFs, pyrrole is polymerized on the BC/c-MWCNTs nano composite membrane by an electrochemical polymerization method to obtain the BC/c-MWCNTs/PPy nano composite membrane; in order to further improve the detection sensitivity of the lactic acid, Cu-MOFs is deposited on the surface of the conductive BC/c-MWCNTs/PPy nano composite membrane by an electrochemical deposition method, and the electrode membrane of the Cu-based flexible non-enzymatic lactic acid sensor is prepared. The electrode membrane has good stability, low cost, long service life, no influence of environment, temperature, pH and the like when detecting lactic acid, and is easy to store. Through detection, the concentration of lactic acid in human sweat can be effectively reflected in real time, and whether the exercise is excessive or not can be judged.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of an electrode film of a Cu-based flexible non-enzymatic lactate sensor is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a conductive BC/c-MWCNTs nano composite membrane: preparing a c-MWCNTs suspension with a preset concentration; pretreating the BC membrane, then soaking the pretreated BC membrane in the c-MWCNTs suspension for ultrasonic treatment for 4-6 h, taking out and cleaning to prepare a conductive BC/c-MWCNTs nano composite membrane;
s2, preparing a BC/c-MWCNTs/PPy nano composite membrane: preparing pyrrole monomer solution; clamping the conductive BC/c-MWCNTs nano composite membrane by using an electrode clamp to serve as a working electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking the pyrrole monomer solution as an electrolyte to perform electrochemical polymerization reaction, and after the polymerization is finished, performing vacuum drying treatment at the temperature of 60-80 ℃ to obtain the BC/c-MWCNTs/ppy nano composite membrane;
s3, preparing an electrode film of the Cu-based flexible non-enzymatic lactate sensor: preparing a copper plating solution; clamping the BC/c-MWCNTs/PPy nano composite membrane by using an electrode clamp to serve as a working electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, and taking the copper plating solution as an electrolyte to perform electrochemical deposition reaction, so as to generate a layer of Cu-MOFs on the BC/c-MWCNTs/PPy nano composite membrane; and then drying the film after the deposition reaction to prepare the Cu-based flexible non-enzymatic lactate sensor electrode film.
2. The method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor according to claim 1, wherein: in step S2, the preparation process of the pyrrole monomer solution is: dissolving 0.05-0.09M lithium perchlorate and 0.01-0.03 wt% soluble starch in 0.05-0.2M phosphate buffer solution, stirring for 15-45 min, adding 0.14-0.28M pyrrole into the mixed solution, and completely mixing to obtain a pyrrole monomer solution.
3. The method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor according to claim 1, wherein: in step S2, the electrochemical polymerization process is set as follows: an electrochemical workstation is used as a reaction device, a constant voltage method is adopted, the reaction potential is set to be 0.6-1.0V, and the reaction time is set to be 120-180 s.
4. The method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor according to claim 1, wherein: in step S3, the preparation process of the copper plating solution is: dissolving 1, 3, 5-benzene tricarbonic acid in N, N-dimethylformamide to obtain a solution A; dissolving triethylamine hydrochloride and copper sulfate trihydrate with a predetermined ratio in water to obtain a solution B; and uniformly mixing the solution A and the solution B to prepare the copper plating solution.
5. The method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor according to claim 4, wherein: in the copper plating solution, the molar ratio of 1, 3, 5-benzene tricarboxylic acid, triethylamine hydrochloride and copper sulfate trihydrate is (0.0005-0.002): (0.0001-0.0003): (0.01-0.03).
6. The method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor according to claim 1, wherein: in step S3, the process of electrochemical deposition is set as: an electrochemical workstation is used as a reaction device, a constant voltage method is adopted, the reaction potential is set to be-0.3 to-0.7 v, and the reaction time is set to be 5 to 15 min.
7. The method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor according to claim 1, wherein: in step S1, the preparation process of the c-MWCNTs suspension is: firstly, preparing a uniform suspension of c-MWCNTs with the concentration of 0.5-2 mg/mL, adding a predetermined amount of hexadecyl ammonium bromide, and performing ultrasonic dispersion for 4-6 hours under an ultrasonic process with the power of 200-400W and the frequency of 30-50 kHz to obtain the suspension of the c-MWCNTs.
8. The method for preparing an electrode film of a Cu-based flexible non-enzymatic lactate sensor according to claim 1, wherein: in step S1, the BC membrane pretreatment process includes: soaking the BC membrane in a solution with the concentration of 0.5-2.0 mol.L-1Treating in NaOH solution at a constant temperature of 70-90 ℃ for 1-3 h in a constant-temperature water bath, taking out the treated BC membrane, and rinsing the BC membrane to be neutral by using clear water; next, the cleaned BC film was cut into a predetermined size.
9. A Cu-based flexible non-enzymatic lactate sensor electrode film prepared by the method for preparing a Cu-based flexible non-enzymatic lactate sensor electrode film according to any one of claims 1 to 8, characterized in that: the Cu-based flexible non-enzymatic lactate sensor electrode film is formed by compounding a BC film serving as a flexible carrier and c-MWCNTs serving as a conductive material to obtain a conductive BC/c-MWCNTs nano composite film, and then sequentially performing pyrrole polymerization and Cu-MOFs deposition on the conductive BC/c-MWCNTs nano composite film by an electrochemical deposition method.
10. The Cu-based flexible non-enzymatic lactate sensor electrode film according to claim 9, wherein: the detection range of the electrode film of the Cu-based flexible non-enzymatic lactate sensor is 0.5-20mM of lactate concentration.
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