Monatomic palladium / carbon nanotube composite membrane as well as preparation method and application thereof
The single-atom palladium/carbon nanotube composite membrane prepared by arc discharge method in electrochemical sensors solves the problems of low sensitivity and complex operation of amitriptyline detection in the prior art, and accurately monitor and rapid detection of amitriptyline are achieved.
Patent Information
- Application Number
- CN202411835202.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-13
- Publication Date
- 2025-03-21
AI Technical Summary
The prior art has not yet found that the detection of amitriptyline (AMI) is performed by electrochemical analysis, and there are shortcomings such as small detection range, low sensitivity, cumbersome operation, expensive instruments or time-consuming sample processing.
The arc discharge method is used to recombine single-atom palladium into carbon nanotubes, and a single-atom palladium/carbon nanotube composite film is prepared, and modified onto the carbon electrode to form an electrochemical sensor to achieve the detection of amitriptyline.
It realizes accurate monitoring and efficient catalytic degradation of amitriptyline, and can quickly detect amitriptyline. It has the advantages of easy portability and simple operation. It is suitable for drug safety and clinical medical treatment.
Smart Images
Figure CN119666962A_ABST
Abstract
Description
Technical Field
[0001] The present application belongs to the field of electrochemical analysis and detection technology, and in particular relates to a single-atom palladium / carbon nanotube composite film and a preparation method and application thereof. Background Art
[0002] Amitriptyline (AMI) is a tricyclic antidepressant. Its pharmacological effect in treating depression mainly works by blocking the reabsorption of norepinephrine (NE) and 5-hydroxytryptamine (5-HT). It also blocks neurotransmitters such as acetylcholine (Ach) and histamine (H). It can be used to treat enuresis, migraine, diabetic peripheral neuropathy, etc. However, excessive use can cause the adverse consequences of poisoning. Therefore, accurate detection of the content of amitriptyline in drugs is of great significance for controlling drug quality and ensuring patient safety.
[0003] At present, the commonly used analytical methods for measuring amitriptyline mainly include high performance liquid chromatography, gas chromatography, mass spectrometry, electrochemical analysis and thin layer chromatography, but these methods have the disadvantages of small detection range, low sensitivity, complicated operation, expensive required instruments or time-consuming sample processing. Among them, electrochemical analysis has the characteristics of high sensitivity, fast analysis speed, simple instrument, easy operation and low cost, and has been widely used in the determination of amitriptyline (AMI). However, the detection of amitriptyline (AMI) by electrochemical analysis has not yet been found. Summary of the invention
[0004] The present application discloses a single-atom palladium / carbon nanotube composite film and a preparation method and application thereof, aiming to solve the technical problem of detecting amitriptyline (AMI) by electrochemical analysis method which has not been found in the prior art.
[0005] In order to achieve the above purpose, the technical solution of this application is:
[0006] A first aspect of the present application provides a single-atom palladium / carbon nanotube composite film, comprising: a carbon nanotube substrate and single-atom palladium on the carbon nanotube substrate.
[0007] In combination with the first aspect, preferably, the molar ratio of the carbon nanotubes to the single-atom palladium is 5:1-3.
[0008] The second aspect of the present application provides a method for preparing the single-atom palladium / carbon nanotube composite film according to the first aspect, the preparation method comprising:
[0009] The single-atom palladium is compounded into carbon nanotubes by an arc discharge method, thus obtaining a single-atom palladium / carbon nanotube composite film.
[0010] In combination with the second aspect, preferably, the arc discharge method comprises:
[0011] Under vacuum conditions, protective gas is filled in, carbon nanotubes containing palladium source are composited to carbon electrode rods as anodes, pure carbon electrode rods are used as cathodes, power is applied, and peeling is performed on the anode surface to obtain single-atom palladium / carbon nanotube composite films.
[0012] In combination with the second aspect, preferably, the protective gas filled is helium, argon or a combination thereof.
[0013] In combination with the second aspect, preferably, the pressure of the protective gas filled is 26-76 kPa.
[0014] In combination with the second aspect, preferably, the discharge current during power-on is controlled within a range of 80-120A.
[0015] The third aspect of the present application provides an electrochemical sensor made of the single-atom palladium / carbon nanotube composite film described in the first aspect or the single-atom palladium / carbon nanotube composite film prepared by the preparation method described in the second aspect, comprising a working electrode, a counter electrode and a reference electrode;
[0016] The working electrode is a carbon electrode modified by the single-atom palladium / carbon nanotube composite film;
[0017] The counter electrode is a platinum wire electrode;
[0018] The reference electrode is a mercury / mercury oxide electrode.
[0019] The fourth aspect of the present application provides the use of the electrochemical sensor described in the third aspect in the catalytic degradation reaction of amitriptyline.
[0020] Compared with the prior art, the advantages or beneficial effects of the embodiments of the present application include at least:
[0021] The single-atom palladium / carbon nanotube composite film provided by the present application includes a carbon nanotube substrate and single-atom palladium on the carbon nanotube substrate; on the one hand, it can give the electrochemical sensor excellent conductivity and flexibility, and has strong adhesion to the carbon electrode surface without the use of adhesives; on the other hand, through the synergistic effect of single-atom palladium and carbon nanotubes, it can give accurate monitoring of amitriptyline and achieve efficient catalytic degradation of amitriptyline. At the same time, it can achieve rapid detection of amitriptyline, has the advantages of being easy to carry and simple to operate, and has broad application prospects in drug safety and clinical medicine. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments recorded in the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.
[0023] Figure 1 XRD diagram of the A1-monoatom palladium / carbon nanotube composite film provided in the examples of the present application;
[0024] Figure 2 This is a SEM image of the A1-monoatom palladium / carbon nanotube composite film provided in the examples of the present application;
[0025] Figure 3 This is a Raman spectrum of the A1-monoatom palladium / carbon nanotube composite film provided in the embodiment of the present application;
[0026] Figure 4 This is a cyclic voltammetry curve of the A1-single atom palladium / carbon nanotube composite film provided in an embodiment of the present application. DETAILED DESCRIPTION
[0027] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.
[0028] In the following description of this embodiment, the term "and / or" is used to describe the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, B exists alone, and A and B exist at the same time. A and B can be singular or plural. The character " / " generally indicates that the associated objects before and after are in an "or" relationship.
[0029] In the following description of this embodiment, the term "at least one" refers to one or more, and "plurality" refers to two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b or c", or "at least one of a, b and c", can all represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.
[0030] Those skilled in the art should understand that in the following description of the embodiments of the present application, the order of serial numbers does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
[0031] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "an" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.
[0032] Those skilled in the art will appreciate that the numerical ranges in the examples of the present application are to be understood as also specifically disclosing each intermediate value between the upper and lower limits of the range. Each smaller range between the intermediate values in any stated value and stated range and any other stated value or intermediate value in the range is also included in the present application. The upper and lower limits of these smaller ranges may be independently included or excluded in the scope.
[0033] Unless otherwise stated, the technical / scientific terms used herein have the same meanings as those generally understood by those skilled in the art in the field described in the present application. Although the present application only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the embodiments or test cases of the present application. All documents mentioned in this specification are generally incorporated by reference to disclose and describe the methods and / or materials related to the documents. In the event of a conflict with any incorporated document, the content of the present application shall prevail.
[0034] It should be noted that all raw materials and reagents in the examples of the present application were purchased on the market or prepared according to conventional methods well known to those skilled in the art.
[0035] In a first aspect, an embodiment of the present application provides a single-atom palladium / carbon nanotube composite film, comprising: a carbon nanotube substrate and single-atom palladium on the carbon nanotube substrate.
[0036] On the one hand, it can give the electrochemical sensor excellent conductivity and flexibility, and strong adhesion to the carbon electrode surface without the need for adhesives; on the other hand, through the synergistic effect of single-atom palladium and carbon nanotubes, it can achieve accurate monitoring of amitriptyline and achieve efficient catalytic degradation of amitriptyline. At the same time, it can achieve rapid detection of amitriptyline, has the advantages of being easy to carry and simple to operate, and has broad application prospects in drug safety and clinical medicine.
[0037] In the embodiment of the present application, the molar ratio of the carbon nanotubes to the single-atom palladium is preferably 5: 1-3, and more preferably 5: 2. Among them, by controlling the molar ratio of the carbon nanotubes to the single-atom palladium, through the synergistic effect of the two, it is possible to achieve accurate monitoring of amitriptyline and achieve efficient catalytic degradation of amitriptyline.
[0038] The second aspect of the present application provides a method for preparing the single-atom palladium / carbon nanotube composite film according to the first aspect, the preparation method comprising:
[0039] The single-atom palladium is compounded into carbon nanotubes by an arc discharge method, thus obtaining a single-atom palladium / carbon nanotube composite film.
[0040] In the embodiment of the present application, the arc discharge method includes: under vacuum conditions, filling with protective gas, compounding carbon nanotubes containing palladium source onto carbon electrode rods as anodes, using pure carbon electrode rods as cathodes, applying power, and peeling off on the surface of the anode to obtain single-atom palladium / carbon nanotube composite films.
[0041] In the embodiment of the present application, the protective gas filled is one of helium and argon or a combination thereof; the pressure of the protective gas filled is 26-76 kPa. By injecting the protective gas, unnecessary impurities are avoided during the reaction. And controlling the pressure of the protective gas filled can control the reaction rate.
[0042] In the embodiment of the present application, the discharge current during power-on is controlled to be 80-120 A. By controlling the discharge current during power-on, the single-atom palladium can be effectively controlled to be evenly and stably distributed on the surface of the carbon nanotube.
[0043] In the third aspect, an embodiment of the present application also provides an electrochemical sensor made of the single-atom palladium / carbon nanotube composite film described in the first aspect or the single-atom palladium / carbon nanotube composite film prepared by the preparation method described in the second aspect, comprising a working electrode, a counter electrode and a reference electrode; the working electrode is a carbon electrode modified by the single-atom palladium / carbon nanotube composite film; the counter electrode is a platinum wire electrode; and the reference electrode is a mercury / mercury oxide electrode.
[0044] In a fourth aspect, the present application also provides an application of the electrochemical sensor described in the third aspect in the catalytic degradation reaction of amitriptyline. It can realize accurate monitoring of amitriptyline and efficient catalytic degradation of amitriptyline, and has a wide range of application prospects in the catalytic degradation reaction of amitriptyline.
[0045] The technical solution of the present application will be further described below in conjunction with specific embodiments.
[0046] Example 1
[0047] This embodiment provides a method for preparing an Al-monoatom palladium / carbon nanotube composite film, which specifically includes:
[0048] S101: using helium at a pressure of 53.2 kPa as a protective gas, discharging between an anode carbon electrode rod containing palladium chloride and a cathode carbon electrode rod, the distance between the anode and the cathode is controlled at 5 mm, the discharge current is 80 A, and the ratio of the number of palladium atoms to the total number of atoms of the anode carbon electrode rod containing the palladium catalyst is 20%, to obtain a single-atom palladium / carbon nanotube composite material;
[0049] S102: The obtained composite material is heated to 450°C and kept warm for 30 minutes, immersed in 12 mol / L hydrochloric acid for 1 hour, taken out and washed with deionized water until neutral and dried, placed in deionized water and stirred evenly to form a suspension, and the prepared single-atom palladium / carbon nanotube composite material suspension is filtered by negative pressure filtration onto the same side of a polytetrafluoroethylene microporous filter membrane (pore size of 2 μm), and after drying, the carbon nanotube membrane is removed from the microporous filter membrane to obtain an A1-single-atom palladium / carbon nanotube composite membrane.
[0050] Example 2
[0051] This embodiment provides a method for preparing an A2-monoatom palladium / carbon nanotube composite film, which specifically includes:
[0052] S201: using helium at a pressure of 53.2 kPa as a protective gas, discharging between an anode carbon electrode rod containing palladium chloride and a cathode carbon electrode rod, the distance between the anode and the cathode is controlled at 5 mm, the discharge current is 80 A, and the ratio of the number of palladium atoms to the total number of atoms of the anode carbon electrode rod containing the palladium catalyst is 40%, to obtain a single-atom palladium / carbon nanotube composite material;
[0053] S202: The obtained composite material is heated to 450°C and kept warm for 30 minutes, immersed in 12 mol / L hydrochloric acid for 1 hour, taken out and washed with deionized water until neutral and dried, placed in deionized water and stirred evenly to form a suspension, and the prepared single-atom palladium / carbon nanotube composite material suspension is filtered by negative pressure filtration onto the same side of a polytetrafluoroethylene microporous filter membrane (pore size of 2 μm), and after drying, the carbon nanotube membrane is removed from the microporous filter membrane to obtain an A2-single-atom palladium / carbon nanotube composite membrane.
[0054] Example 3
[0055] This embodiment provides a method for preparing an A3-monoatom palladium / carbon nanotube composite film, which specifically includes:
[0056] S301: using helium with a pressure of 53.2 kPa as a protective gas, discharging between an anode carbon electrode rod containing palladium chloride and a cathode carbon electrode rod, the distance between the anode and the cathode is controlled at 5 mm, the discharge current is 80 A, and the ratio of the number of palladium atoms to the total number of atoms of the anode carbon electrode rod containing the palladium catalyst is 60%, to obtain a single-atom palladium / carbon nanotube composite material;
[0057] S302: The obtained composite material is heated to 450°C and kept warm for 30 minutes, immersed in 12 mol / L hydrochloric acid for 1 hour, taken out and washed with deionized water until neutral and dried, placed in deionized water and stirred evenly to form a suspension, and the prepared single-atom palladium / carbon nanotube composite material suspension is filtered by negative pressure filtration onto the same side of a polytetrafluoroethylene microporous filter membrane (pore size of 2 μm), and after drying, the carbon nanotube membrane is removed from the microporous filter membrane to obtain an A3-single-atom palladium / carbon nanotube composite membrane.
[0058] At the same time, in order to verify the comprehensive performance of the single-atom palladium / carbon nanotube composite film prepared in the above examples, the present application provides the following comparative examples for detailed description.
[0059] Comparative Example 1
[0060] The material provided in the comparative example of the present application is subjected to comparative testing using pure carbon nanotubes without compounding single atomic palladium.
[0061] In order to verify the structural characteristics of the prepared single-atom palladium / carbon nanotube composite film, XRD, SEM, and Raman spectroscopy tests were performed on the single-atom palladium / carbon nanotube composite film. Figure 1-Figure 3 shown.
[0062] according to Figure 1 It can be seen that the A2-single atom palladium / carbon nanotube composite film was tested by X-ray diffraction (XRD) spectra. Figure 1 The diffraction peak of palladium can be seen in the figure, but there are no diffraction peaks of other elements, indicating that the metal elements in the palladium-loaded single-walled carbon nanotube flexible electrode have been completely oxidized after heat treatment in dry air.
[0063] according to Figure 2 It can be seen that the scanning electron microscope (SEM) image of A2-single atom palladium / carbon nanotube composite film is Figure 2 It can be seen that the particle size of the palladium-containing single-walled carbon nanotubes is very small, and the surface is not covered by a carbon film. Fibrous objects can be seen in the figure, which are the palladium-containing single-walled carbon nanotubes.
[0064] according to Figure 3 It can be seen that this is the Raman spectrum of A2-single atom palladium / carbon nanotube composite film. Figure 3 The splitting of the G peak (1520-1590cm-1 ) and a strong radial breathing peak (140-165cm -1 ), D peak (1320cm -1 ) and G peak (1590cm -1 ) intensity ratio is very small, indicating that the single-walled carbon nanotubes containing palladium have high crystallinity.
[0065] In order to verify the electrochemical performance of the prepared single-atom palladium / carbon nanotube composite film, a catalytic test was performed on the single-atom palladium / carbon nanotube composite film. The single-atom palladium / carbon nanotube composite film prepared in the example was composited on the carbon electrode and the single-walled carbon nanotube flexible electrode prepared in Comparative Example 1 was tested for catalytic activity on the oxidation reaction of amitriptyline. Test conditions: the working electrode, the counter electrode, and the reference electrode were the corresponding flexible electrodes (in the shape of a disc with a diameter of 8 mm), platinum sheets, and mercury / mercury oxide electrodes, respectively. The electrolyte contained 0.4 mol / L sodium hydroxide and 1 mmol / L amitriptyline, and the scanning rate was 20 mV / s. The test results are shown in Tables 1 and Figure 4 .
[0066] Table 1 Electrochemical behavior of single-atom palladium / carbon nanotube composite films
[0067]
[0068]
[0069] According to Table 1, when the ratio of the number of palladium atoms in the single-atom palladium / carbon nanotube composite film to the total number of atoms in the anode carbon electrode rod containing the palladium catalyst is 40%, the current of the oxidation peak is optimal.
[0070] according to Figure 4 It can be seen that an obvious amitriptyline oxidation current peak can be observed at 0.42V for the flexible electrode made of the A2-single-atom palladium / carbon nanotube composite film prepared in Example 2, indicating that the palladium-loaded single-walled carbon nanotube flexible electrode has significant catalytic activity for the electrocatalytic oxidation of amitriptyline; while the single-walled carbon nanotube flexible electrode prepared in Comparative Example 1 has no obvious catalytic activity for the electrocatalytic oxidation of amitriptyline.
[0071] Therefore, the single-atom palladium / carbon nanotube composite film provided by the present application includes a carbon nanotube substrate and single-atom palladium on the carbon nanotube substrate; it can give the electrochemical sensor excellent conductivity and flexibility, and has strong adhesion to the carbon electrode surface without the use of adhesives; and through the synergistic effect of single-atom palladium and carbon nanotubes, it can give accurate monitoring of amitriptyline and achieve efficient catalytic degradation of amitriptyline. At the same time, it can achieve rapid detection of amitriptyline, has the advantages of being easy to carry and simple to operate, and has broad application prospects in drug safety and clinical medicine.
[0072] The various embodiments in this specification are described in a progressive manner, and the same or similar parts between the various embodiments can be referenced to each other, and each embodiment focuses on the differences from other embodiments.
[0073] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit the present application. Although the present application has been described in detail with reference to the aforementioned embodiments, a person of ordinary skill in the art should understand that the technical solutions recorded in the aforementioned embodiments may still be modified, or some or all of the technical features therein may be replaced by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the present application.
Claims
1. A single-atom palladium / carbon nanotube composite film, characterized in that: include: A carbon nanotube substrate and single-atom palladium on the carbon nanotube substrate.
2. The single-atom palladium / carbon nanotube composite film according to claim 1, characterized in that: The molar ratio of the carbon nanotubes to the single-atom palladium is 5:1-3.
3. A method for preparing a single-atom palladium / carbon nanotube composite film according to any one of claims 1 to 2, characterized in that: The preparation method comprises: The single-atom palladium is compounded into carbon nanotubes by an arc discharge method, thus obtaining a single-atom palladium / carbon nanotube composite film.
4. The method for preparing the single-atom palladium / carbon nanotube composite film according to claim 3, characterized in that: The arc discharge method comprises: Under vacuum conditions, protective gas is filled in, carbon nanotubes containing palladium sources are composited to carbon electrode rods as anodes, pure carbon electrode rods are used as cathodes, electricity is applied, and single-atom palladium / carbon nanotube composite materials are obtained by peeling off on the surface of the anode; The single-atom palladium / carbon nanotube composite material is calcined at high temperature, placed in water to form a suspension, and filtered under negative pressure to obtain the single-atom palladium / carbon nanotube composite membrane.
5. The method for preparing a single-atom palladium / carbon nanotube composite film according to claim 4, characterized in that: The protective gas filled is helium, argon or a combination thereof.
6. The method for preparing a single-atom palladium / carbon nanotube composite film according to claim 4, characterized in that: The pressure of the protective gas filled is 26-76 kPa.
7. The method for preparing a single-atom palladium / carbon nanotube composite film according to claim 4, characterized in that: The palladium source is one or more of palladium chloride, palladium nitrate, palladium sulfate and palladium acetate.
8. The method for preparing a single-atom palladium / carbon nanotube composite film according to claim 4, characterized in that: The discharge current during power-on is controlled at 80-120A.
9. An electrochemical sensor made of the single-atom palladium / carbon nanotube composite film according to any one of claims 1 to 2 or the single-atom palladium / carbon nanotube composite film prepared by the preparation method according to any one of claims 3 to 8, characterized in that: It includes working electrode, counter electrode and reference electrode; The working electrode is a carbon electrode modified by the single-atom palladium / carbon nanotube composite film; The counter electrode is a platinum wire electrode; The reference electrode is a mercury / mercury oxide electrode.
10. Use of the electrochemical sensor according to claim 9 in the catalytic degradation reaction of amitriptyline.