Locally asymmetric one-dimensional atomic chain material and preparation method and application thereof
By introducing platinum atoms with locally asymmetric structures into Mo1.33C, a zigzag one-dimensional atomic chain material was prepared, which solved the problems of low sensitivity and poor stability of existing dopamine detection methods and achieved dopamine detection with high sensitivity, rapid response and strong anti-interference ability.
Patent Information
- Application Number
- CN202510863860.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-25
- Publication Date
- 2025-09-19
AI Technical Summary
Existing dopamine detection methods have narrow detection range, low sensitivity, and poor selectivity. In particular, they lack stability in complex environments, cannot accurately detect low concentrations of dopamine, and are easily interfered with by other substances.
A locally asymmetric one-dimensional atomic chain material was used. By partially replacing molybdenum atoms with platinum atoms in Mo1.33C, a locally asymmetric structure was formed. A zigzag material was prepared by combining etching, stripping and heat treatment processes to increase active sites and improve detection sensitivity and selectivity.
It achieves high-sensitivity detection of dopamine at low concentrations, with fast response time and good stability. It can accurately detect and resist interference in complex environments, thereby improving detection efficiency and real-time performance.
Smart Images
Figure CN120664546A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of electric sensing materials, and in particular to a locally asymmetric one-dimensional atomic chain material and a preparation method and application thereof. Background Art
[0002] Dopamine, as an important neurotransmitter in the central nervous system and other parts of the body, plays a variety of key roles in the brain. Abnormal dopamine levels and function are closely related to various neurological and psychiatric diseases, such as Parkinson's disease, Alzheimer's disease and schizophrenia. Therefore, accurate detection of dopamine is of great significance for the effective diagnosis, prevention and treatment of these diseases. Currently, methods for detecting dopamine include colorimetry, chromatography, chemiluminescence, etc., which usually require complex and expensive equipment or long detection time. In contrast, electrochemical sensing analysis methods have been widely used in the field of dopamine detection due to their advantages such as low detection cost and simple operation.
[0003] Sensing materials used in traditional technologies for dopamine detection include metal and metal oxide nanomaterials, carbon nanotubes, graphene, and reduced graphene oxide. However, these materials often face multiple limitations in terms of dispersibility, selectivity, stability, and preparation costs for biosensing applications. Conventional electrochemical dopamine sensors prepared from these materials still suffer from narrow detection ranges, poor sensitivity, and detection limits. Their selectivity is largely affected by interference from other coexisting substances (such as ascorbic acid and uric acid), making them unable to meet the needs of extreme environments.
[0004] Currently, a transition metal carbide (Mo) that is chemically ordered in a plane 1.33 C) is widely used in energy storage, supercar capacitors, catalysis, water purification, actuators and sensors due to its excellent conductivity, hydrophilicity and electrochemical activity. 1.33 C has good electrochemical properties, but when detecting dopamine target molecules, the detection signal is weak and cannot accurately detect dopamine at low concentrations; in the presence of other interfering substances, it is not stable enough and exhibits low selectivity, resulting in inaccurate detection results. Summary of the Invention
[0005] The present invention aims to provide a locally asymmetric one-dimensional atomic chain material, its preparation method, and its application. The locally asymmetric one-dimensional atomic chain material provided by the present invention can accurately detect dopamine with high sensitivity, strong stability and anti-interference ability in complex environments.
[0006] In order to achieve the above object, the present invention provides the following technical solutions:
[0007] A locally asymmetric one-dimensional atomic chain material, including Mo 1.33C and partial replacement of Mo 1.33 C of platinum atoms in molybdenum atoms.
[0008] Preferably, the mass percentage of platinum atoms in the locally asymmetric one-dimensional atomic chain material is 1.7-2.3%.
[0009] The present invention provides a method for preparing the locally asymmetric one-dimensional atomic chain material described in the above technical solution, comprising the following steps:
[0010] The hydrogen fluoride solution and (Mo 2 / 3 Sc 1 / 3 )2AlC powder is mixed and etched to obtain multilayer Mo 1.33 C;
[0011] The multilayer Mo 1.33 C is mixed with a stripping agent and subjected to stripping treatment to obtain a single layer of Mo 1.33 C;
[0012] The single layer Mo 1.33 C is mixed with chloroplatinic acid hexahydrate and subjected to adsorption treatment to obtain a composite powder;
[0013] The composite powder is heat-treated in an inert-reducing mixed atmosphere to obtain the locally asymmetric one-dimensional atomic chain material.
[0014] Preferably, the mass concentration of the hydrogen fluoride solution is 10-15%, and the hydrogen fluoride solution and (Mo 2 / 3 Sc 1 / 3 )The dosage ratio of 2AlC powder is 15-25mL:1g; the etching treatment time is 70-74h.
[0015] Preferably, the multilayer Mo 1.33 The usage ratio of C to the stripping agent is 0.1 g: 0.5-1.5 mL, and the stripping agent includes tetrabutylammonium hydroxide or trimethylamine oxide; and the stripping treatment time is 4-6 minutes.
[0016] Preferably, the single layer Mo 1.33 The mass ratio of C to chloroplatinic acid hexahydrate is 100:4-6.
[0017] Preferably, the inert-reducing mixed atmosphere comprises argon and 1% by volume of hydrogen.
[0018] Preferably, the heat treatment temperature is 480-520° C., the holding time is 0.5-2 h, and the rate of heating to the heat treatment temperature is 8-10° C. / min.
[0019] The present invention provides a dopamine sensor, comprising the locally asymmetric one-dimensional atomic chain material described in the above technical solution or the locally asymmetric one-dimensional atomic chain material prepared by the preparation method.
[0020] The present invention provides the use of the locally asymmetric one-dimensional atomic chain material described in the above technical solution or the locally asymmetric one-dimensional atomic chain material prepared by the preparation method or the dopamine sensor in detecting dopamine.
[0021] The present invention provides a locally asymmetric one-dimensional atomic chain material, including Mo 1.33 C and partial replacement of Mo 1.33 C is composed of platinum atoms and molybdenum atoms in the molybdenum atoms. The asymmetric one-dimensional atomic chain material provided by the present invention is zigzag-shaped, and the platinum atoms replace part of the molybdenum atoms to form a local asymmetric structure. The local asymmetric structure enables the local asymmetric one-dimensional atomic chain material to have more types and quantities of active sites, which is beneficial to improving the sensitivity and accuracy of dopamine detection. The dopamine sensor constructed by the local asymmetric one-dimensional atomic chain material of the present invention has high sensitivity, lower detection limit and fast response time compared with other types of sensors. It can effectively detect dopamine at low concentrations, has a short response time, and can improve detection efficiency and real-time performance. At the same time, the local asymmetric one-dimensional atomic chain material maintains good stability during a longer working time (7 days), and has unique advantages in particular for work with high sensitivity requirements. In the presence of other interfering substances, the local asymmetric one-dimensional atomic chain material has good anti-interference ability, high selectivity for dopamine, and accurate detection results.
[0022] The present invention provides a method for preparing an asymmetric one-dimensional atomic chain material. The present invention adopts an etching method to (Mo 2 / 3Sc 1 / 3 )2AlC Sc and Al are completely etched to obtain multilayer Mo 1.33 C, Mo 1.33 C lattice structure has a high concentration of vacancy defects; multilayer Mo 1.33 C is stripped in the presence of a stripping agent to obtain a single layer of Mo 1.33 C nanosheets and / or multilayer Mo 1.33 C; then hexahydrate chloroplatinic acid was introduced, and platinum atoms replaced Mo 1.33 Part of the molybdenum atoms in C are finally converted into an asymmetric one-dimensional atomic chain material. The preparation method provided by the present invention is simple to operate and has mild reaction conditions. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 This is an electron microscope image of the spherical aberration of a locally asymmetric one-dimensional atomic chain material;
[0024] Figure 2Schematic diagram of dopamine sensing test using locally asymmetric one-dimensional atomic chain materials;
[0025] Figure 3 This is the response time diagram of the locally asymmetric one-dimensional atomic chain material;
[0026] Figure 4 is the stability diagram of a locally asymmetric one-dimensional atomic chain material;
[0027] Figure 5 This is the specific response diagram of the locally asymmetric one-dimensional atomic chain material. DETAILED DESCRIPTION
[0028] The present invention provides a locally asymmetric one-dimensional atomic chain material, including Mo 1.33 C and partial replacement of Mo 1.33 C of platinum atoms in molybdenum atoms.
[0029] In one embodiment of the present invention, the mass percentage of platinum atoms in the locally asymmetric one-dimensional atomic chain material is 1.7-2.3%, and the locally asymmetric one-dimensional atomic chain material has a zigzag shape. This locally asymmetric structure provides the locally asymmetric one-dimensional atomic chain material with a greater variety and number of active sites, which helps improve the sensitivity and accuracy of dopamine detection.
[0030] The present invention provides a method for preparing the locally asymmetric one-dimensional atomic chain material described in the above technical solution, comprising the following steps:
[0031] The hydrogen fluoride solution and (Mo 2 / 3 Sc 1 / 3 )2AlC powder is mixed and etched to obtain multilayer Mo 1.33 C;
[0032] The multilayer Mo 1.33 C is mixed with a stripping agent and subjected to stripping treatment to obtain a single layer of Mo 1.33 C;
[0033] The single layer Mo 1.33 C is mixed with chloroplatinic acid hexahydrate and subjected to adsorption treatment to obtain a composite powder;
[0034] The composite powder is heat-treated in an inert-reducing mixed atmosphere to obtain the locally asymmetric one-dimensional atomic chain material.
[0035] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.
[0036] The present invention combines hydrogen fluoride solution and (Mo 2 / 3 Sc 1 / 3)2AlC powder is mixed and etched to obtain multilayer Mo 1.33 C. As an embodiment of the present invention, the mass concentration of the hydrogen fluoride solution can be 10% to 15%, specifically 10%; the hydrogen fluoride (HF) solution and (Mo 2 / 3 Sc 1 / 3 )2AlC powder can be used in an amount of 15 to 25 mL: 1 g, specifically 20 mL: 1 g; the present invention replaces fresh HF solution every 24 hours to ensure that "Sc" and "Al" can be completely etched; the etching treatment time can be 70 to 74 hours, specifically 72 hours; after the etching treatment is completed, the reaction system is filtered and washed to obtain a multilayer Mo 1.33 C. The present invention has no special limitation on the filtration. The present invention washes the filtered precipitate with water, and the washing times may be 5 to 6 times. The water may be deionized water. The present invention has no special limitation on the washing process, and the washing process may be performed until the pH value of the precipitate is close to neutral.
[0037] Get multilayer Mo 1.33 After C, the present invention will be said multilayer Mo 1.33 C is mixed with a stripping agent and subjected to stripping treatment to obtain a single layer of Mo 1.33 C. As an embodiment of the present invention, the stripping agent can be tetrabutylammonium hydroxide (TBAOH) or trimethylamine oxide (TMAOH), preferably tetrabutylammonium hydroxide; the multilayer Mo 1.33 The amount ratio of C to the stripping agent can be 0.1g:0.5~1.5mL, specifically 0.1g:1mL; the stripping treatment includes oscillation, and the stripping treatment time can be 4~6min, specifically 5min; after the stripping treatment, the mixture is further centrifuged and washed; the centrifugal speed can be 5500~6500rpm, specifically 6000rpm, the time can be 4~6min, specifically 5min, and the number of centrifugation is preferably 3 times. The present invention centrifuges the mixture to remove the stripping agent; the present invention washes the solid after centrifugation with water and filters to obtain a single layer Mo 1.33 C.
[0038] Obtained single-layer Mo 1.33 After C, the present invention will be the single layer Mo 1.33 C is mixed with chloroplatinic acid hexahydrate (H2PtCl6·6H2O) and subjected to adsorption treatment to obtain composite powder. As an embodiment of the present invention, the present invention is to mix a single layer of Mo 1.33 C was dispersed in water and ultrasonically treated to obtain Mo 1.33 C dispersion, the Mo 1.33The concentration of the C dispersion can be 4 mg / mL, and the ultrasonic time can be 25 to 35 minutes, specifically 30 minutes; the present invention dissolves chloroplatinic acid hexahydrate in water to obtain a 10 mg / mL stock solution; the Mo 1.33 Monolayer Mo in C dispersion 1.33 The mass ratio of C to chloroplatinic acid hexahydrate in the stock solution can be 100:4-6, specifically 100:5. The mixing is performed in an ice bath for 2-4 hours, specifically 3 hours. After the mixing, the mixed dispersion is vacuum filtered and freeze-dried to obtain a composite powder. The vacuum filtration and freeze-drying are not particularly limited in the present invention.
[0039] After obtaining the composite powder, the present invention heat treats the composite powder in an inert-reducing mixed atmosphere to obtain the locally asymmetric one-dimensional atomic chain material. As one embodiment of the present invention, the inert-reducing mixed atmosphere comprises argon and 1% hydrogen by volume. The heat treatment temperature can be 480-520°C, specifically 500°C, for 0.5-2 hours, specifically 1 hour, and the heating rate to the heat treatment temperature can be 8-10°C / min. The heat treatment is performed in a tube furnace.
[0040] The present invention provides a dopamine sensor, comprising the locally asymmetric one-dimensional atomic chain material described in the above technical solution or the locally asymmetric one-dimensional atomic chain material prepared by the preparation method.
[0041] The present invention provides the use of the locally asymmetric one-dimensional atomic chain material described in the above technical solution or the locally asymmetric one-dimensional atomic chain material prepared by the preparation method or the dopamine sensor in detecting dopamine.
[0042] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0043] Example 1
[0044] Put 1g(Mo 2 / 3 Sc 1 / 3 )2AlC powder was immersed in 20 mL of 10 wt.% HF aqueous solution and etched at room temperature under magnetic stirring for 72 h, with fresh HF aqueous solution replaced every 24 h; the reaction system was filtered to obtain a precipitate, which was washed 5 to 6 times with deionized water until the pH value was close to neutral to obtain a multilayer Mo 1.33 C; to 0.1g multilayer Mo 1.331 mL of tetrabutylammonium hydroxide was added to C, and the stripping treatment was carried out under shaking conditions for 5 minutes. The mixture was centrifuged at 6000 rpm for 5 minutes and repeated three times. The solid after centrifugation was collected, washed with water and filtered to collect the monolayer Mo 1.33 C powder.
[0045] 0.1 g of the prepared single-layer Mo 1.33 C powder was dispersed in 25 mL of water and Mo 1.33 The C suspension was ultrasonically treated for 30 min; 0.1 g H2PtCl6·6H2O was dissolved in 10 mL of water to obtain 10 mg·mL -1 500 μL of stock solution was added dropwise to the Mo 1.33 C suspension, stirred in an ice bath environment for 3 hours; the reaction system was vacuum filtered to obtain a solid, and the obtained solid was freeze-dried to obtain a powder; the obtained powder was placed in a tubular furnace, and a mixed gas of argon and hydrogen (the volume fraction of hydrogen is 1%) was introduced, and heated to 500°C at a heating rate of 10°C / min and maintained for 1 hour to obtain a locally asymmetric one-dimensional atomic chain material.
[0046] Test Example 1
[0047] The locally asymmetric one-dimensional atomic chain material obtained in Example 1 was scanned by spherical aberration electron microscope. The results are as follows: Figure 1 shown. Figure 1 This is a spherical aberration electron microscope image of a locally asymmetric one-dimensional atomic chain material. Figure 1 It can be seen that the atomic chain structure of the locally asymmetric one-dimensional atomic chain material is serrated.
[0048] Test Example 2
[0049] The locally asymmetric one-dimensional atomic chain material obtained in Example 1 was used as a dopamine sensor for dopamine sensing test. The locally asymmetric one-dimensional atomic chain material was prepared into dopamine sensors with different concentrations (0.1-100 μM); 2 mg of test material (locally asymmetric one-dimensional atomic chain material), 100 μL Nafion (5wt%) and 900 μL ethanol were ultrasonically treated for 15 minutes to prepare a uniform ink; the prepared ink (10 μL) was loaded onto an L-glassy carbon electrode with a diameter of 3 mm as a working electrode. On a CHI 660E electrochemical workstation, with a graphite rod as the counter electrode and an Ag / AgCl electrode (saturated KCl) as the reference electrode, electrochemical measurements were performed in a three-electrode system, including cyclic voltammetry (CV), linear sweep voltammetry (LSV), differential pulse voltammetry (DPV) and chronopotentiometry, to study the response current corresponding to different concentrations of locally asymmetric one-dimensional atomic chain materials. The results are shown in Figure 2. Figure 2 shown. Figure 2Schematic diagram of dopamine sensing test using locally asymmetric one-dimensional atomic chain materials. Figure 2 It shows that under the potential conditions of 0.15~0.6V and in the concentration range of 0.1~100μM, the current response values of local asymmetric one-dimensional atomic chain materials with different concentrations are different and show a linear relationship.
[0050] Test Example 3
[0051] The response speed of the locally asymmetric one-dimensional atomic chain material obtained in Example 1 to dopamine was tested. Dopamine was dropped into a blank phosphate buffer solution, and the locally asymmetric one-dimensional atomic chain material prepared in Example 1 was placed into the above solution. The curve change of the local asymmetric one-dimensional atomic chain material in the presence of time and current response was observed. The results are shown in FIG. Figure 3 shown. Figure 3 This is the response time diagram of the locally asymmetric one-dimensional atomic chain material. Figure 3 It can be seen that the current response time is 1.8s, indicating that the locally asymmetric one-dimensional atomic chain material responds quickly to dopamine.
[0052] Test Example 4
[0053] The locally asymmetric one-dimensional atomic chain material obtained in Example 1 was used for dopamine sensing for 7 consecutive days. The response current results of the locally asymmetric one-dimensional atomic chain material over 7 days are shown in FIG. Figure 4 shown. Figure 4 is the stability diagram of the locally asymmetric one-dimensional atomic chain material. Figure 4 It can be seen that the current detected by the local asymmetric one-dimensional atomic chain material as a dopamine sensor has been maintained above 90 μA for 7 consecutive days, indicating that the local asymmetric one-dimensional atomic chain material prepared by the present invention can maintain good stability during a longer working time (7 days).
[0054] Test Example 5
[0055] The anti-interference ability of the local asymmetric one-dimensional atomic chain material obtained in Example 1 to different analytes was studied. The dopamine solution was divided into 7 groups on average. The dopamine content in each group was the same. One of the groups was used as a blank control. The same content of potassium chloride, sodium chloride, epinephrine, fructose, glucose and ascorbic acid were added to the other six groups of dopamine solutions in sequence. The local asymmetric one-dimensional atomic chain material was placed in the 7 groups of solutions in sequence, and the current response of the local asymmetric one-dimensional atomic chain material was detected. The results are shown in Figure 2. Figure 5 shown. Figure 5 is the specific response diagram of the locally asymmetric one-dimensional atomic chain material. Figure 5It can be seen that in the presence of different interferents, the current of the detected dopamine is not much different from the current of dopamine without interferents, indicating that the asymmetric one-dimensional atomic chain material has good anti-interference ability and high selectivity for dopamine.
[0056] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.
Claims
1. A locally asymmetric one-dimensional atomic chain material, including Mo 1.33 C and partial replacement of Mo 1.33 C of platinum atoms in molybdenum atoms.
2. The locally asymmetric one-dimensional atomic chain material according to claim 1, characterized in that: The mass percentage of platinum atoms in the locally asymmetric one-dimensional atomic chain material is 1.7-2.3%.
3. The method for preparing the locally asymmetric one-dimensional atomic chain material according to claim 1 or 2, comprising the following steps: The hydrogen fluoride solution and (Mo 2 / 3 Sc 1 / 3 )2AlC powder is mixed and etched to obtain multilayer Mo 1.33 C; The multilayer Mo 1.33 C is mixed with a stripping agent and subjected to stripping treatment to obtain a single layer of Mo 1.33 C; The single layer Mo 1.33 C is mixed with chloroplatinic acid hexahydrate and subjected to adsorption treatment to obtain a composite powder; The composite powder is heat-treated in an inert-reducing mixed atmosphere to obtain the locally asymmetric one-dimensional atomic chain material.
4. The preparation method according to claim 3, characterized in that The mass concentration of the hydrogen fluoride solution is 10-15%, and the hydrogen fluoride solution and (Mo 2 / 3 Sc 1 / 3 )The dosage ratio of 2AlC powder is 15-25mL:1g; the etching treatment time is 70-74h.
5. The preparation method according to claim 3, characterized in that The multilayer Mo 1.33 The usage ratio of C to the stripping agent is 0.1 g: 0.5-1.5 mL, and the stripping agent includes tetrabutylammonium hydroxide or trimethylamine oxide; and the stripping treatment time is 4-6 minutes.
6. The preparation method according to claim 3, characterized in that The single layer Mo 1.33 The mass ratio of C to chloroplatinic acid hexahydrate is 100:4-6.
7. The preparation method according to claim 3, characterized in that The inert-reducing mixed atmosphere includes argon and 1% by volume of hydrogen.
8. The preparation method according to claim 3, characterized in that The heat treatment temperature is 480-520° C., the heat preservation time is 0.5-2 hours, and the rate of heating to the heat treatment temperature is 8-10° C. / min.
9. A dopamine sensor comprising the locally asymmetric one-dimensional atomic chain material according to claim 1 or 2 or the locally asymmetric one-dimensional atomic chain material prepared by the preparation method according to any one of claims 3 to 8.
10. Use of the locally asymmetric one-dimensional atomic chain material according to claim 1 or 2, or the locally asymmetric one-dimensional atomic chain material prepared by the preparation method according to any one of claims 3 to 8, or the dopamine sensor according to claim 9 in detecting dopamine.