Preparation method and application of chalcogenide doped graphdiyne

Abstract

The invention discloses a preparation method and application of chalcogenide doped graphdiyne, chalcogenide is implanted into a chalcogenide cavity in a simple thermal driving mode by using a chalcogenide cavity formed in para-nitrogen substituted graphdiyne as an anchoring site, so that the chalcogenide is distributed in a lattice shape, and a high-load monatomic graphdiyne material is obtained. The nano-enzyme sensor is constructed by utilizing the activity of peroxidase-like enhanced by the chalcogenide doped graphdiyne to detect bisphenol and thiosulfate ions, and powerful support is provided for monitoring of food safety and environmental safety.

Description

Technical Field

[0001] The present invention relates to a preparation method and application of chalcogen-doped graphdiyne, belonging to the technical field of graphdiyne-based nanozymes. Background Art

[0002] Nanozymes are artificially synthesized nanomaterials that can mimic the activities of natural enzymes, aiming to solve the limitations of natural enzymes in terms of stability and cost performance. Currently, a variety of materials have been found to have enzyme-like catalytic abilities, such as metal particles, oxide particles, carbon family materials, metal-organic framework materials, etc. Modification and modification of these materials are also important means to improve their activities.

[0003] Graphdiyne is a two-dimensional material formed by the ordered arrangement of sp and sp 2 hybridized carbons according to certain rules, and is an allotrope of carbon together with graphene, carbon nanotubes, etc. Due to the rich pore structure and large conjugated system in graphdiyne, it has good stability, high specific surface area, excellent thermal and electrical conductivity, and some other unique physical and chemical properties, so it is widely used in the fields of energy, catalysis, etc. Traditional graphdiyne materials contain only carbon element, which hinders the improvement of its catalytic performance to a certain extent. Therefore, doping with one or more new elements for modification is an effective means. Some of the currently reported works are mostly difficult to accurately control the doping sites, and the product structures are not uniform.

[0004] In Patent CN 109772413 B, under the same protective atmosphere, the nitrogen source and sulfur source are separately placed upstream of the carbon source or the nitrogen-sulfur source is placed upstream of the carbon source, and the temperature is programmed to 700-1000 °C to obtain nitrogen-sulfur co-doped graphdiyne. In the graphdiyne synthesized by this preparation method, sulfur elements are doped on the benzene ring, while some nitrogen elements are doped on the alkyne bond, and the doping sites are relatively random and non-uniform.

[0005] In Patent Application CN 116284058 A, 2,5,8-tris(4-ethynylphenyl)benzotriazole is prepared using a heterocycle containing thiazole and an alkynylation reagent as raw materials, and then nitrogen-sulfur co-doped graphdiyne is prepared by a coupling reaction under the catalysis of copper. This method has precise doping sites, but the preparation period is long and the steps are numerous, which is not suitable for large-scale preparation.

[0006] In Patent Application CN 115448286 A, high-temperature reduction technology is selected to prepare cobalt, nitrogen co-doped γ-type graphdiyne. The doping method is simple and no post-treatment is required, but the doping site of cobalt is not clear, which is not conducive to subsequent mechanism analysis.

[0007] In existing patents, there is no method to dope chalcogens into graphdiyne by simple and general means to form graphdiyne nanozymes with well-defined single atoms at specific sites. However, a synthetic method for constructing effective doping sites is necessary. Summary of the Invention

[0008] The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art. The present invention provides a preparation method and application of chalcogen-doped graphdiyne, which solves the technical problems such as inaccurate control of graphdiyne doping sites or cumbersome preparation steps.

[0009] To achieve the above purpose, the present invention adopts the following technical solutions:

[0010] 1. A preparation method of chalcogen-doped graphdiyne, the specific steps are as follows:

[0011] (1) First, mix and grind the chalcogen element simple substance and para-nitrogen-substituted graphdiyne to obtain a mixture;

[0012] (2) Then, place the mixture in a porcelain boat, heat-treat it under nitrogen protection, and naturally cool it to room temperature (25°C) to obtain a powder material;

[0013] (3) Finally, wash and dry the powder material to obtain the chalcogen-doped graphdiyne;

[0014] Among them, the chalcogen element simple substance is selenium powder or tellurium powder.

[0015] As one of the preferred technical solutions, in step (1), the para-nitrogen-substituted graphdiyne is prepared by a ball-milling method using pyrazine and calcium carbide as raw materials.

[0016] As a further preferred technical solution, the mass ratio of pyrazine to calcium carbide is 1:5; the ball-milling conditions are: ball-milling at 600 rpm for 8 hours under an Ar inert atmosphere.

[0017] As a further preferred technical solution, post-treatment is carried out after ball-milling. The specific method of post-treatment is: wash three times with 1 mol / L nitric acid solution, distilled water, and absolute ethanol respectively, vacuum-dry at 60°C for 12 - 16 hours to obtain a dried sample; then, disperse the dried sample in absolute ethanol and perform ultrasonic treatment for 12 hours; finally, centrifuge to collect the precipitate and dry it for 12 - 16 hours.

[0018] As one of the preferred technical solutions, in step (1), the mass ratio of the chalcogen element simple substance to the para-nitrogen-substituted graphdiyne is 6 - 10:1.

[0019] As one of the preferred technical solutions, in step (1), mix and grind in a mortar for 30 minutes.

[0020] As one of the preferred technical solutions, in step (2), the specific method of heat treatment is as follows: heating up to the target temperature at a heating rate of 5 °C / min and holding for 3 hours; when the elemental chalcogen is selenium powder, the target temperature is 800 °C, and when the elemental chalcogen is tellurium powder, the target temperature is 900 °C.

[0021] As one of the preferred technical solutions, in step (3), the washing method is as follows: washing three times each with 1 mol / L nitric acid solution, distilled water, and absolute ethanol in sequence.

[0022] As one of the preferred technical solutions, in step (3), the drying method is as follows: drying in vacuum at 60 °C for 12 - 16 hours.

[0023] 2. A chalcogen-doped graphdiyne is obtained by the aforementioned preparation method.

[0024] 3. Application of the aforementioned chalcogen-doped graphdiyne in constructing a nanozyme sensor.

[0025] 4. A nanozyme sensor constructed by using the aforementioned chalcogen-doped graphdiyne.

[0026] 5. Application of the aforementioned chalcogen-doped graphdiyne or nanozyme sensor in the detection of bisphenols and thiosulfate ions in liquid samples in the field of food or water quality detection.

[0027] As one of the preferred technical solutions, when the chalcogen is selenium, the corresponding chalcogen-doped graphdiyne or nanozyme sensor is used for thiosulfate detection; when the chalcogen is tellurium, the corresponding chalcogen-doped graphdiyne or nanozyme sensor is used for bisphenol detection.

[0028] As one of the preferred technical solutions, application of the aforementioned chalcogen-doped graphdiyne or nanozyme sensor in the detection of bisphenols and thiosulfate ions in liquid samples in the field of food or water quality detection.

[0029] As one of the further preferred technical solutions, the food is the liquid in canned products.

[0030] As one of the preferred technical solutions, the bisphenols include but are not limited to: bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenolic acid; the thiosulfates include but are not limited to sodium thiosulfate.

[0031] Advantages of the present invention:

[0032] The present invention utilizes the checkerboard-shaped cavities formed in para-nitrogen-substituted graphdiyne as the anchoring sites, implants chalcogen elements into the cavities by a simple heat-driven method, and makes them distributed in a dot matrix pattern to obtain a high-loading single-atom graphdiyne material. By using its enhanced peroxidase-like activity, a nanozyme sensor is constructed for the detection of bisphenol and thiosulfate ions, providing strong support for the monitoring of food safety and environmental safety.

[0033] The key raw material of the present invention is para-nitrogen-substituted graphdiyne. Specifically, pyrazine and calcium carbide are used as raw materials, and two carbon atoms at the para-position of the benzene ring are replaced by nitrogen atoms, so as to form a checkerboard-shaped cavity in the graphdiyne structure, pre-designing clear doping sites for the doping of chalcogen elements and effectively realizing precise doping with a high loading amount.

[0034] In the present invention, the implantation of single atoms does not change the lamellar structure of the graphdiyne precursor, and enhances its peroxidase-like activity. The present invention uses a simple and general heat-driven method to synthesize graphdiyne doped with chalcogen elements at fixed points, enabling the chalcogen elements to achieve a high-loading dot matrix distribution therein, enhancing its enzyme-like activity, and the constructed colorimetric sensor has the potential for practical applications.

[0035] Another object of the present invention is to provide the application of the above-mentioned graphdiyne materials with different nitrogen doping amounts in expressing peroxidase-like activity and constructing an antioxidant recognition sensing array. This material has good peroxidase-like activity, and the constructed sensing array can effectively recognize antioxidants. Description of the Drawings

[0036] Figure 1 Schematic diagram of the synthesis of chalcogen (tellurium)-doped graphdiyne prepared in Example 1 of the present invention;

[0037] Figure 2 XRD patterns of chalcogen (tellurium, selenium)-doped graphdiyne prepared in Examples 1-2 of the present invention;

[0038] Figure 3 HRTEM image of chalcogen (selenium)-doped graphdiyne prepared in Example 2 of the present invention;

[0039] Figure 4 UV absorbance bar chart of the activity comparison between chalcogen (tellurium, selenium)-doped graphdiyne nanozymes prepared in Examples 1-2 of the present invention and sulfur-doped graphdiyne nanozymes prepared in Comparative Example 1;

[0040] Figure 5 UV spectra of the activity comparison of chalcogen (tellurium)-doped graphdiyne at different heating temperatures prepared in Examples 1, 5-6 of the present invention;

[0041] Figure 6Ultraviolet spectrum for the activity comparison of chalcogen (selenium)-doped graphdiyne at different heating temperatures prepared in Examples 2, 7 - 8 of the present invention;

[0042] Figure 7 Ultraviolet spectrum for the activity comparison and absorbance histogram of chalcogen (tellurium)-doped graphdiyne with different mass ratios of chalcogen element simple substance to para-nitrogen-substituted graphdiyne prepared in Examples 1, 3 - 4 of the present invention;

[0043] Figure 8 Ultraviolet absorbance histogram for the activity comparison between the para-nitrogen-substituted graphdiyne nanozyme prepared in Examples 1 - 2 of the present invention and the common nitrogen source (melamine)-calcined ordinary nitrogen-doped graphdiyne nanozyme used in Comparative Example 2;

[0044] Figure 9 Ultraviolet spectrum of chalcogen (tellurium)-doped graphdiyne prepared in Example 1 of the present invention in the presence of different concentrations of bisphenol AF;

[0045] Figure 10 Different responses of chalcogen (tellurium)-doped graphdiyne prepared in Example 1 of the present invention to five bisphenols at a concentration of 800 μM under two colorimetric channels (TMB and OPD);

[0046] Figure 11 Ultraviolet spectrum of chalcogen (selenium)-doped graphdiyne prepared in Example 2 of the present invention in the presence of different concentrations of sodium thiosulfate. Detailed implementation manners

[0047] The present invention will be further described below in conjunction with the drawings and examples. It should be noted that the following description is only for explaining the present invention and does not limit its content.

[0048] Reference Example (para-nitrogen-substituted graphdiyne):

[0049] A mixture of 2.5 g of calcium carbide, 0.5 g of pyrazine, and 25 g of zirconia grinding beads with a particle size of 5 mm was placed in a ball mill jar and sealed. A high-speed ball mill was used to ball mill at a speed of 600 rpm for 8 h. This process was carried out under an Ar inert atmosphere to prevent the introduction of O2 and water. After the grinding process was completed, it was washed three times with 1 mol / L nitric acid solution, distilled water, and absolute ethanol respectively, and vacuum dried at 60 °C for 16 h. Subsequently, the dried sample was dispersed in absolute ethanol at a ratio of 0.1 g:100 mL and ultrasonic treatment was carried out for 12 h using an ultrasonic material disperser at a power ratio of 55%, with the program set to on for 2 s and off for 1 s. After ultrasonic treatment, the precipitate was centrifuged and dried for 16 h to obtain the final product para-nitrogen-substituted graphdiyne.

[0050] Example 1 (chalcogen (tellurium)-doped graphdiyne):

[0051] Take 0.05 g of para-nitrogen-substituted graphdiyne and 0.3 g of tellurium powder, grind them in a mortar for 30 min to ensure uniform mixing to obtain a mixture, place it in a porcelain boat, and perform heat treatment under nitrogen protection. The heating conditions are as follows: heat from room temperature to 900 °C at a heating rate of 5 °C / min, hold for 3 h, and then naturally cool to room temperature to obtain a powder material. Wash the powder material three times with 1 mol / L nitric acid solution, distilled water, and absolute ethanol in sequence, and vacuum dry it at 60 °C for 12 h.

[0052] Figure 1 Schematic diagram for the synthesis of chalcogen (tellurium)-doped graphdiyne prepared in Example 1; Figure 3 HRTEM image of chalcogen (selenium)-doped graphdiyne.

[0053] Example 2 (Chalcogen (selenium)-doped graphdiyne):

[0054] Take 0.05 g of para-nitrogen-substituted graphdiyne and 0.3 g of selenium powder, grind them in a mortar for 30 min to ensure uniform mixing to obtain a mixture, place it in a porcelain boat, and perform heat treatment under nitrogen protection. The heating conditions are as follows: heat from room temperature to 800 °C at a heating rate of 5 °C / min, hold for 3 h, and then naturally cool to room temperature to obtain a powder material. Wash the powder material three times with 1 mol / L nitric acid solution, distilled water, and absolute ethanol in sequence, and vacuum dry it at 60 °C for 12 h.

[0055] Figure 2 XRD patterns of chalcogen (selenium, tellurium)-doped graphdiyne prepared in Example 1 and Example 2.

[0056] Example 3 (Chalcogen (tellurium)-doped graphdiyne (different mass ratios of chalcogen element simple substance to para-nitrogen-substituted graphdiyne)):

[0057] Take 0.5 g of tellurium powder to make the mass ratio of chalcogen element simple substance to para-nitrogen-substituted graphdiyne 10:1; the rest is the same as Example 1.

[0058] Example 4 (Chalcogen (tellurium)-doped graphdiyne (different mass ratios of chalcogen element simple substance to para-nitrogen-substituted graphdiyne)):

[0059] Take 0.4 g of tellurium powder to make the mass ratio of chalcogen element simple substance to para-nitrogen-substituted graphdiyne 8:1; the rest is the same as Example 1.

[0060] Example 5 (Chalcogen (tellurium)-doped graphdiyne (different heating temperatures)):

[0061] The heating temperature is 800 °C; the rest is the same as Example 1.

[0062] Example 6 (Chalcogen (tellurium)-doped graphdiyne (different heating temperatures)):

[0063] The heating temperature is 1000 °C; the rest is the same as in Example 1.

[0064] Example 7 (Chalcogen (selenium) doped graphdiyne (different heating temperatures)):

[0065] The heating temperature is 700 °C; the rest is the same as in Example 2.

[0066] Example 8 (Chalcogen (selenium) doped graphdiyne (different heating temperatures)):

[0067] The heating temperature is 900 °C; the rest is the same as in Example 2.

[0068] Comparative Example 1 (Sulfur doped graphdiyne)

[0069] Take 0.05 g of para-nitrogen substituted graphdiyne and 0.3 g of sulfur powder, grind them in a mortar for 30 min to ensure uniform mixing to obtain a mixture, place it in a porcelain boat, and carry out heat treatment under nitrogen protection. The heating conditions are as follows: heat from room temperature to 600 °C at a heating rate of 5 °C / min, keep the temperature for 3 h, and then naturally cool to room temperature to obtain a powder material. Wash the powder material three times with 1 mol / L nitric acid solution, distilled water, and absolute ethanol respectively, and vacuum dry it at 60 °C for 12 h.

[0070] Comparative Example 2 (Ordinary nitrogen doped graphdiyne)

[0071] Take 0.05 g of graphdiyne and 0.5 g of melamine, grind them in a mortar for 30 min to ensure uniform mixing to obtain a mixture, place it in a porcelain boat, and carry out heat treatment under nitrogen protection. The heating conditions are as follows: first heat from room temperature to 300 °C at a heating rate of 10 °C / min, then heat from 300 °C to 800 °C at a heating rate of 5 °C / min, keep the temperature for 1 h, and then naturally cool to room temperature to obtain a powder material. Wash the powder material three times with 1 mol / L nitric acid solution, distilled water, and absolute ethanol respectively, and vacuum dry it at 60 °C for 12 h.

[0072] Disperse the chalcogen (selenium, tellurium) doped graphdiyne prepared in Examples 1-2 and the sulfur doped graphdiyne prepared in Comparative Example 1 into ethanol solutions at a concentration of 1 mg / mL respectively. Take 50 μL of graphdiyne nanozyme, 50 μL of hydrogen peroxide (mass concentration 1%), and 50 μL of 3,3',5,5'-tetramethylbenzidine (20 mM) and add them to an acetic acid-sodium acetate buffer solution system with a total volume of 3 mL, incubate at 45 °C for 15 minutes, and use a TU-1901 UV-visible spectrophotometer to measure the absorption signal at a specific wavelength, and then measure its peroxidase-like (POD) and oxidase-like (OXD) activities. The reagents involved above are purchased from Shanghai Macklin Reagents. Figure 4The results show that the activity of selenium- and tellurium-doped graphdiyne is significantly better than that of sulfur-doped graphdiyne, demonstrating excellent doping effects.

[0073] Comparing the POD activities of the chalcogen (tellurium)-doped graphdiyne prepared in Examples 1, 5, and 6, Figure 5 the results show that graphdiyne has the highest activity when the heating temperature is 900 °C. After the above screening, the heating temperature of the prepared chalcogen (tellurium)-doped graphdiyne is determined to be 900 °C.

[0074] Comparing the POD activities of the chalcogen (selenium)-doped graphdiyne prepared in Examples 2, 7, and 8, Figure 6 the results show that graphdiyne has the highest activity when the heating temperature is 800 °C. After the above screening, the heating temperature of the prepared chalcogen (selenium)-doped graphdiyne is determined to be 800 °C.

[0075] Comparing the POD activities of the chalcogen (tellurium)-doped graphdiyne prepared in Examples 1, 3, and 4, Figure 7 the results show that when the mass ratio of the chalcogen element to para-nitrogen-substituted graphdiyne is 6 - 10:1, the activities of the prepared doped graphdiyne are similar. After the above screening, the mass ratio of the chalcogen element to para-nitrogen-substituted graphdiyne is determined to be 6 - 10:1.

[0076] Figure 8 The results show that the activity of the nanozyme synthesized using para-nitrogen-substituted graphdiyne is significantly higher than that of the ordinary non-site-specific nitrogen-doped graphdiyne nanozyme obtained by calcining with a common nitrogen source (melamine) in Comparative Example 2, confirming the enhancing effect of the positioning anchor on the activity.

[0077] Introduce 60 μL of bisphenol solution into the test system, and use bisphenol substances with different concentrations (0, 1, 5, 10, 20, 50, 100, 200, 500, 800, 1000 μM) (bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol acid, all purchased from Shanghai Titan Scientific Co., Ltd.) to study the different inhibitory degrees on the peroxidase-like activity of the chalcogen (tellurium)-doped graphdiyne nanozyme prepared in Example 1 (as Figure 9 shown) and the differences in the inhibitory degrees of different types of bisphenol substances at the same concentration (as Figure 10 shown). Through two colorimetric channels of TMB and OPD, use a UV-visible spectrophotometer to collect the absorption peaks at 450 and 652 nm as colorimetric signals, construct a colorimetric nanozyme sensor, and achieve sensitive, rapid, and quantitative detection of bisphenol substances, providing an effective method for the detection of pollutants in food.

[0078] The chalcogen (selenium)-doped graphdiyne nanozyme prepared in Example 2 completed the detection of thiosulfate (sodium thiosulfate, purchased from Shanghai Titan Scientific Co., Ltd.) at different concentrations (0, 5, 10, 20, 30, 50, 100, 200, 250, 300 μM) using a similar principle as above (as Figure 11 shown). The intensity of the absorbance at 652 nm decreased with the increase in the concentration of the analyte thiosulfate, and there was a linear relationship, indicating that the sensor constructed with the chalcogen-doped graphdiyne nanozyme prepared in Example 2 can be used for the monitoring of pollutants in the water environment.

[0079] Although the specific embodiments of the present invention have been described above in conjunction with the accompanying drawings, it is not a limitation of the protection scope of the present invention. Based on the technical solutions of the present invention, various modifications or deformations that can be made by those skilled in the art without creative efforts are still within the protection scope of the present invention.

Claims

1. A method for preparing chalcogenide-doped graphyne, characterized in that: The specific steps are as follows: (1) firstly, a chalcogen element and para-nitrogen-substituted graphyne are mixed and ground to obtain a mixture; (2) The mixture is then placed in a porcelain boat, heated under nitrogen protection, and naturally cooled to room temperature to obtain a powder material; (3) finally washing and drying the powder material to obtain the chalcogenide-doped graphyne; Wherein, the chalcogen element single substance is selenium powder or tellurium powder.

2. The preparation method according to claim 1, characterized in that: In step (1), the para-nitrogen-substituted graphyne is prepared by ball milling using pyrazine and calcium carbide as raw materials.

3. The preparation method according to claim 1, characterized in that: In step (1), the mass ratio of the chalcogen element to the para-nitrogen substituted graphyne is 6 to 10:

1.

4. The preparation method according to claim 1, characterized in that: In step (1), the mixture is mixed and ground in a mortar for 30 minutes.

5. The preparation method according to claim 1, characterized in that: In step (2), the specific method of heating treatment is: heating to the target temperature at a heating rate of 5°C / min and keeping warm for 3 hours; when the chalcogen element is selenium powder, the target temperature is 800°C, and when the chalcogen element is tellurium powder, the target temperature is 900°C.

6. The preparation method according to claim 1, characterized in that: In step (3), the washing method is: washing three times with 1 mol / L nitric acid solution, distilled water and anhydrous ethanol respectively; The drying method is: vacuum drying at 60°C for 12 to 16 hours.

7. A chalcogenide-doped graphene, characterized in that: The invention is obtained by the preparation method according to any one of claims 1 to 6.

8. Use of the chalcogenide-doped graphyne described in claim 7 in constructing a nanozyme sensor.

9. A nanozyme sensor constructed using the chalcogen element-doped graphyne as described in claim 7.

10. Use of the chalcogen element-doped graphyne described in claim 7 or the nanoenzyme sensor described in claim 9 in the detection of bisphenol and thiosulfate ions.

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