CN115180600A - Method for preparing nanosheet with large area-diameter ratio - Google Patents

Method for preparing nanosheet with large area-diameter ratio Download PDF

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CN115180600A
CN115180600A CN202210928895.XA CN202210928895A CN115180600A CN 115180600 A CN115180600 A CN 115180600A CN 202210928895 A CN202210928895 A CN 202210928895A CN 115180600 A CN115180600 A CN 115180600A
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sodium chloride
nanosheet
carbon
diameter ratio
large area
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李晓丹
刘宏宇
何瑞
王�锋
孟诗云
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Chongqing Technology and Business University
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    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0605—Binary compounds of nitrogen with carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • C01P2004/00—Particle morphology
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    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like

Abstract

The application relates to the field of carbon nano materials, and discloses a method for preparing g-C with a large area-diameter ratio 3 N 4 A method of nanosheet. Fully grinding the carbon-nitrogen-rich small molecular compound and sodium chloride, and then treating the ground mixture at high temperature to obtain the large area-diameter ratio g-C with an in-plane highly-ordered structure 3 N 4 A nanosheet. The application adopts a sodium chloride method to prepare g-C with a structure with a large area-diameter ratio 3 N 4 The preparation method is simple and convenient, has low cost and high yield, is suitable for industrial mass production, and has high use value.The carbon nitride is synthesized while a large-area two-dimensional sheet structure is kept, the thickness of the nanosheet is only 2-10nm, the transverse size is kept between 5-30 mu m, and the nanosheet has a very high application prospect in the fields of catalysis, corrosion prevention, capacitance and the like.

Description

Method for preparing nanosheet with large area-diameter ratio
Technical Field
The application relates to the field of carbon nano materials, in particular to a method for preparing g-C with large area-diameter ratio 3 N 4 A method of nanoplatelets.
Background
Graphite-like carbon nitride (g-C) 3 N 4 ) The graphene-like polymer semiconductor is of a graphene-like structure and is formed by stacking sheets. g-C 3 N 4 The nanosheet serving as a typical layered two-dimensional sheet material has the characteristics of good thermal stability, chemical resistance, more active sites and the like, and a great deal of research work is used for exploring the application of graphite-phase carbon nitride (such as photocatalysis, corrosion prevention and the like) in different fields, so that the nanosheet is a new two-dimensional material. There are currently many ways to strip bulk carbon nitride into g-C 3 N 4 The nano-sheets are mainly divided into physical methods and chemical methods, wherein the physical methods comprise secondary calcination, solution ultrasonic stripping, ball milling and the like, and the chemical methods comprise alkali stripping, acid stripping, thermal oxidant etching and the like, but the methods have the defects of long operation time, low yield, complex process and the like, and most importantly, the methods inevitably cause low surface-to-surface ratio nano-sheets during operation, thereby preventing potential application in many directions.
g-C of large face-to-face ratio 3 N 4 The nano-sheet has higher surface area and higher oxidation-reduction potential, improves the electron transmission capability along the in-plane direction, and can fully exert the photocatalytic activity in the catalytic field; as one of the two-dimensional sheets, the barrier performance of the sheet is required to be exerted in the field of corrosion prevention, and a large area-to-diameter ratio is very necessary, so that the sheet can realize a barrier to corrosive substances to the greatest extent; in addition, large area to diameter ratio organism g-C 3 N 4 The nano-sheet has extremely good biocompatibility, so that the nano-sheet has good potential in the fields of biological imaging, drug carriers and the like. Thus, g-C was developed which was easy to handle and had a large aspect ratio 3 N 4 The preparation method is of great importance.
Disclosure of Invention
In view of the above, the present application aims to provide a method for preparing g-C with large area-diameter ratio 3 N 4 The method of the nano-sheet enables the nano-sheet to be capable of preparing a large-area-diameter-ratio g-C3N4 nano-sheet with the transverse dimension reaching micron level and the thickness only being nano level;
it is another object of the present application to provide a method for preparing a large aspect ratio g-C 3 N 4 Method for preparing nanosheets having a large aspect ratio g-C 3 N 4 When the nano sheet is used for modifying the epoxy resin coating, the ultraviolet resistance of the coating can be improved.
To solve the above technical problems/achieve the above object or at least partially solve the above technical problems/achieve the above object, the present application provides a method for preparing a large aspect ratio g-C 3 N 4 A method of nanoplatelet comprising:
fully grinding the carbon-nitrogen-rich small molecular compounds and sodium chloride, and then treating the ground mixture at high temperature to obtain the large aspect ratio g-C with a highly ordered structure in the plane 3 N 4 Nanosheets.
Surface polymerization is a successful bottom-up method for preparing sp2 carbon nanostructures, with appropriate solid surfaces available to promote agglomeration and orientation of building blocks to build nanosheet structures. According to the method, the carbon-nitrogen-rich micromolecular compound is adopted to carry out surface polymerization on the surface of the sodium chloride crystal, the sodium chloride crystal with high surface energy is beneficial to the adsorption and activation of the carbon-nitrogen-rich micromolecular compound on the surface of the sodium chloride crystal, the kinetic hindrance of condensation reaction is reduced, and then the unique interaction of the sodium chloride crystal, the carbon-nitrogen-rich micromolecular compound and a derivative intermediate thereof causes strong interface constraint, so that the 2D nanosheet structure is directionally assembled on the surface of the sodium chloride crystal.
Preparing the large area-diameter ratio g-C 3 N 4 In the nanosheet process, the larger the area of sodium chloride (the more the amount is used), the more favorable the surface polymerization is, and the g-C with the large area-diameter ratio is formed 3 N 4 A nanosheet. Optionally, the mass ratio of the carbon-nitrogen-rich small molecular compound to the sodium chloride is 1. In certain embodiments of the present application, the mass ratio of the carbon-nitrogen-rich small molecule compound to sodium chloride is 1; in some other embodiments of the present application, the mass ratio of the carbon-nitrogen-rich small molecule compound to sodium chloride is 1.
Optionally, the carbon-nitrogen-rich small molecule compound is melamine, dicyandiamide, urea or thiourea.
Optionally, the elevated temperature is increased at a rate of 5-10 ℃.
Optionally, the elevated temperature is from 500 to 600 ℃; in certain embodiments of the present application, the elevated temperature is 550 ℃.
Optionally, the method further comprises a process of cooling to room temperature after the treatment at the high temperature for washing to remove sodium chloride and drying the nanosheets. In certain embodiments of the present application, the washing is a deionized water washing.
In still other embodiments of the present application, the drying is vacuum drying at 40-80 ℃ for 12-24 hours. Wherein, the drying temperature can be 60 ℃, and the drying time can be 12 hours.
Large aspect ratio g-C prepared according to the process of the present application 3 N 4 The nano-sheet has a micron-sized transverse dimension which can reach 5-30 μm and a nano-sized thickness which can reach 2-10nm. Small aspect ratio g-C prepared by conventional acid stripping method and direct thermal polymerization method without adding sodium chloride 3 N 4 The transverse size and the thickness of the nano-sheets are both micron-sized;
in addition, the large area-diameter ratio g-C prepared by the method of the application 3 N 4 The MOFs material grafted on the surface of the nanosheet is used for modifying the epoxy resin coating, the modified coating can keep excellent corrosion resistance effect under the ultraviolet irradiation for 300 hours, and the small surface diameter ratio g-C is utilized 3 N 4 The ultraviolet resistance of the nano-sheet modified coating is obviously reduced.
According to the technical scheme, the g-C with the structure with the large area-diameter ratio is prepared by a sodium chloride method 3 N 4 The preparation method of the nano-sheet is simple and convenient, has low cost and high yield, is suitable for industrial mass production, and has high use value. The carbon nitride is synthesized while a large-area two-dimensional sheet structure is kept, the thickness of the nanosheet is only 2-10nm, the transverse dimension is kept between 5-30 mu m, and the carbon nitride composite material has a very high application prospect in the fields of catalysis, corrosion prevention, capacitance and the like.
Drawings
FIG. 1 shows the large area to diameter ratio g-C of example 1 3 N 4 Nanosheets and comparative example 1 directlySmall aspect ratio g-C prepared by thermal polymerization 3 N 4 Nanosheet (b-C) 3 N 4 ) An XRD pattern of (a);
FIG. 2 shows the large area to diameter ratio g-C of example 1 3 N 4 Nanosheet FT-IR spectroscopy;
FIG. 3 shows the large area to diameter ratio g-C of example 1 3 N 4 A nanosheet TEM image;
FIG. 4 shows the large aspect ratio g-C of example 1 3 N 4 A nanosheet SEM image;
FIG. 5 shows the large area to diameter ratio g-C of example 2 3 N 4 A nanosheet TEM image;
FIG. 6 shows the large area to diameter ratio g-C of example 3 3 N 4 A nanosheet TEM image;
FIG. 7 shows the small aspect ratio g-C prepared in comparative example 1 3 N 4 Nanosheet (b-C) 3 N 4 ) SEM picture of (1);
FIG. 8 is a graph showing the small aspect ratio g-C prepared in comparative example 2 3 N 4 Nanosheet (b-C) 3 N 4 ) SEM picture of (1);
FIG. 9 shows NH 2 -MIL-101@g-C 3 N 4 A Bode diagram of EIS of the nano-sheet modified epoxy composite anticorrosive coating;
FIG. 10 shows NH 2 -MIL-125@g-C 3 N 4 A Bode diagram of EIS of the nano-sheet modified epoxy composite anticorrosive coating;
FIG. 11 shows MIL-100@ g-C 3 N 4 And (3) Bode diagram of EIS of the nano-sheet modified epoxy composite anticorrosive coating.
Detailed Description
The application discloses a method for preparing g-C with large area-diameter ratio 3 N 4 The nanosheet method can be realized by appropriately modifying the process parameters by referring to the content in the text. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included in the present application. While the methods described herein have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that the products described herein can be made without departing from the spirit, scope, and content of the present applicationThe techniques, processes and applications described herein may be implemented and utilized with modifications or appropriate alterations and combinations. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that, in this document, if relational terms such as "first" and "second", "step 1" and "step 2", and "(1)" and "(2)" occur, they are only used for distinguishing one entity or operation from another entity or operation, and do not necessarily require or imply any actual relation or order between these entities or operations. Also, 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. Without further limitation, an element defined by the phrases "comprising one of 8230; \8230;" 8230; "does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element. Meanwhile, the embodiments and features in the embodiments may be combined with each other in the present application without conflict.
In certain embodiments of the present application, the large aspect ratio g-C 3 N 4 The nano-sheet is obtained by surface polymerization of a carbon and nitrogen-rich small molecular compound and sodium chloride at high temperature, wherein the carbon and nitrogen-rich small molecular compound is melamine, dicyandiamide, urea or thiourea. Surface polymerization is a successful bottom-up approach to the preparation of sp2 nanostructures, with appropriate solid surfaces available to promote agglomeration and orientation of building blocks to construct nanosheet structures. The method adopts the carbon-nitrogen-rich micromolecule compound to polymerize on the surface of the sodium chloride crystal, and the sodium chloride crystal with high surface energy is beneficial to the adsorption and activation of the carbon-nitrogen-rich micromolecule compound on the surface of the sodium chloride crystal, so that the condensation reaction is reducedThe method has the advantages that the kinetic obstruction is avoided, and meanwhile, strong interface constraint is caused by the unique interaction of the sodium chloride crystal, the carbon-nitrogen-rich micromolecule compound and the derivative intermediate thereof, so that the 2D nanosheet structure is directionally assembled on the surface of the sodium chloride crystal, and the large area-diameter ratio g-C is prepared 3 N 4 A nanosheet.
In certain embodiments of the present application, g-C is produced by acid stripping and direct thermal polymerization without the addition of sodium chloride 3 N 4 The nano-sheet shows that the transverse dimension and the thickness of the nano-sheet are nano-scale, the transverse dimension and the thickness of the nano-sheet are micron-scale, and the nano-sheet and the g-C prepared by the sodium chloride method are similar to those of the nano-sheet prepared by the sodium chloride method 3 N 4 Compared with the nano-sheet, the surface-to-diameter ratio is smaller.
Furthermore, in certain embodiments of the present application, the present application utilizes the large aspect ratio g-C prepared 3 N 4 g-C with large area-diameter ratio prepared by nano-sheet grafting MOFs material and acid stripping method 3 N 4 Comparison of nano-sheet grafted MOFs materials shows that the MOFs @ g-C of the application 3 N 4 The nano composite material can obviously improve the uvioresistant performance of the epoxy resin coating/layer, and shows that the g-C with large aspect ratio 3 N 4 Excellent effect of the nano-sheet.
In each set of comparative experiments provided in the present application, unless otherwise specified, other experimental conditions, materials, etc. are kept consistent for comparability, except for the differences indicated for each set.
A method for preparing a large aspect ratio g-C as provided in the present application 3 N 4 The method of nanosheet is further illustrated.
Example 1: preparation of large surface-diameter ratio g-C by sodium chloride method 3 N 4 Nano-sheet
6g of melamine were thoroughly ground with 30g of sodium chloride using an agate mortar and the mixture was then transferred into a crucible with a lid and heated to 550 ℃ in a muffle furnace at a rate of 5 ℃/min for 4h. Cooling to room temperature, washing with deionized water for several times to remove sodium chloride, and vacuum drying at 60 deg.C for 12 hr to obtain large area diameter ratio g-C with in-plane highly ordered structure 3 N 4 Nanosheet powder.
The results of the test show that: g-C according to XRD pattern (FIG. 1) 3 N 4 The diffraction peaks at 14.2 °, 21.8 °, 28.7 °, 29.9 ° and 36.3 ° are distinct and correspond to the (110), (210), (220), (310) and (320) planes of the polyheptazineimide structure, respectively, indicating g-C 3 N 4 Has high crystallinity. (100) The peak reaction is an in-plane long-range ordered structure between heptazine units, and the (002) peak reaction is interlayer stacking, and an XRD pattern shows that the large area ratio b-C is obtained by direct thermal polymerization in comparison with sodium chloride-free method 3 N 4 This application g-C 3 N 4 The (100) peak of (a) has higher intensity, and the (002) peak becomes broader and weaker, indicating that nano-platelets can be formed by surface polymerization on the surface of sodium chloride crystals.
The g-C was investigated using FT-IR spectroscopy (FIG. 2) 3 N 4 3000 to 3600cm -1 The absorption peak of (A) is an amino group stretch of 900 to 1900cm -1 The absorption peak of (A) is a typical aromatic form g-C 3 N 4 N (-C) in azacycles 3 Or caused by stretching vibration of the C-NH-C bridge, 808cm -1 The absorption peak of (2) is related to the respiratory vibration mode of the heptazine ring unit, 2180cm -1 The vibration peak is obvious and may come from g-C 3 N 4 Amino groups on the surface are bonded. The above results show that g-C 3 N 4 Was successfully synthesized.
From the TEM and SEM images (FIGS. 3-4), it can be seen that g-C 3 N 4 The transverse line size of the nano sheet is in micron level, and the interlayer thickness is in several nanometer level.
Example 2: preparation of large surface-diameter ratio g-C by sodium chloride method 3 N 4 Nano-sheet
5g of urea and 35g of sodium chloride were ground thoroughly with an agate mortar and the mixture was transferred into a crucible with a lid and heated to 550 ℃ in a muffle furnace at a rate of 5 ℃/min for 4h. Cooling to room temperature, washing with deionized water for several times to remove sodium chloride, and vacuum drying at 60 deg.C for 12 hr to obtain large surface diameter ratio g-C with highly ordered structure in surface 3 N 4 Nanosheet powder.
Its XRD spectrumAnd FT-IR spectra identical to those of example 1, with TEM images shown in FIG. 5, g-C 3 N 4 The transverse line size of the nano-sheet is in micron level, and the interlayer thickness is in several nanometer level.
Example 3: sodium chloride method for preparing g-C with large area-diameter ratio 3 N 4 Nano-sheet
5g of dicyandiamide and 20g of sodium chloride were thoroughly ground with an agate mortar, and the mixture was then transferred into a crucible with a lid and heated to 550 ℃ in a muffle furnace at a rate of 5 ℃/min for 4h. Cooling to room temperature, washing with deionized water for several times to remove sodium chloride, and vacuum drying at 60 deg.C for 12 hr to obtain large surface diameter ratio g-C with highly ordered structure in surface 3 N 4 Nanosheet powder.
The XRD pattern and FT-IR spectrum result are the same as those of example 1, the TEM image is shown in FIG. 6, g-C 3 N 4 The transverse line size of the nano sheet is in micron level, and the interlayer thickness is in several nanometer level.
Comparative example 1: preparation of small-area-ratio g-C by sodium chloride-free direct thermal polymerization method 3 N 4 Nano-sheet
10g of melamine were transferred into a crucible with a lid and heated to 550 ℃ in a muffle furnace at a rate of 5 ℃/min for 4h. Cooling to room temperature to obtain light yellow solid, i.e. blocky carbon nitride (b-C) 3 N 4 ). From its SEM image (FIG. 7) it can be seen that both the lateral dimensions and the thickness are in the micrometer range, with the aspect ratio much smaller than g-C 3 N 4 。
Comparative example 2: preparation of small aspect ratio g-C by acid stripping method 3 N 4 Nano-sheet
0.3g of bulk carbon nitride was added to 12ml of H 2 SO 4 Stirring for 1h, slowly adding 150ml of deionized water to obtain a suspension, standing for 24h, performing centrifugal separation, repeatedly washing with water and ethanol for 3 times, and drying at 50 ℃ for 6h to obtain the carbon nitride nanosheet with small surface-to-diameter ratio, which is named as b-C 3 N 4 . As can be seen from the SEM image (FIG. 8), b-C was stripped with sulfuric acid 3 N 4 The transverse dimension of (A) is mostly below 100nm, and the surface-to-diameter ratio is far less than g-C 3 N 4 。
Example 4: g-C with different surface-to-diameter ratios 3 N 4 Detection of ultraviolet resistance of nanosheet to epoxy resin coating/coating
1. g-C of large face-to-face ratio 3 N 4 Nano-sheet
Preparation according to example 1;
2. small aspect ratio g-C 3 N 4 Nano-sheet
Prepared with reference to comparative example 2;
3、NH 2 -MIL-101@g-C 3 N 4 /b-C 3 N 4 preparation of nanocomposites
100mg of g-C prepared in example 1 are initially introduced 3 N 4 Nanosheets or the small aspect ratio b-C prepared in this example 3 N 4 The powder was added to 60ml of DMF and sonicated for 30min. Then 0.25g of 2-aminoterephthalic acid and 0.746g of FeCl 3 ·6H 2 And O is added into the solution, and the ultrasonic treatment is continued for 30min. Then transferring the mixture into a reaction kettle to react for 24 hours at 110 ℃, centrifugally separating precipitates after the reaction is finished, washing the precipitates with DMF (dimethyl formamide) and methanol for a plurality of times, and drying the precipitates in vacuum for 12 hours at 60 ℃ to obtain NH 2 -MIL-101@g-C 3 N 4 /b-C 3 N 4 Nanosheets.
4、NH 2 -MIL-125@g-C 3 N 4 /b-C 3 N 4 Preparation of nanocomposites
100mg of g-C prepared in example 1 are initially introduced 3 N 4 Nanosheets or the small aspect ratio b-C prepared in this example 3 N 4 The powder was added to 45ml of DMF and sonicated for 30min. Then 5ml of methanol was added, and 0.816g of 2-aminoterephthalic acid and 0.45ml of titanium isopropoxide were further added to the above solution, and stirred for 30min. Then transferring the mixture into a reaction kettle to react for 24 hours at the temperature of 150 ℃, centrifugally separating precipitates after the reaction is finished, washing the precipitates for a plurality of times by using DMF (dimethyl formamide) and methanol, and drying the precipitates for 12 hours in vacuum at the temperature of 60 ℃ to obtain NH 2 -MIL-125@g-C 3 N 4 /b-C 3 N 4 。
5、MIL-100@g-C 3 N 4 /b-C 3 N 4 Preparation of nanocomposites
100mg of g-C3N4 nanoplates prepared in example 1 or a small aspect ratio b-C prepared in this example were first prepared 3 N 4 The powder was added to 60ml of deionized water and sonicated for 30min. Then 0.5043g of trimesic acid and 1.454g of Fe (NO) 3 ) 3 ·9H 2 O is added into the solution and stirred for 1h. Then transferring into a reaction kettle for reaction at 160 deg.C for 12h, centrifuging after reaction, washing with deionized water and ethanol for several times, and vacuum drying at 80 deg.C for 12h to obtain MIL-100@ g-C 3 N 4 /b-C 3 N 4 Nanosheets.
6. Preparation of composite coating/coating from nano composite material modified epoxy resin
And adding 0.02g of the prepared three groups (prepared in items 3-5) of nanosheets into 6g of epoxy resin, mechanically stirring for one hour, carrying out ultrasonic treatment in an ice-water bath for 10min, adding 4g of polyamide curing agent, and stirring and mixing uniformly to obtain the uniformly dispersed modified epoxy composite coating. The epoxy composite coating is applied to the surface of low-carbon steel, cured for 3 days at room temperature and further cured for 3 hours at 80 ℃ to obtain the modified epoxy composite coating.
7. Ultraviolet resistance test and results
The modified epoxy composite coating was irradiated under ultraviolet rays having a wavelength of 340nm for 300h, and finally, after being immersed in 3.5wt% NaCl solution for 20 days, its corrosion resistance was evaluated by using an electrochemical workstation (CHI 660E). Further, its absorption of ultraviolet rays was also investigated by an ultraviolet spectrophotometer (UV 2700).
Bode diagram of FIG. 9 shows NH 2 -MIL-101@g-C 3 N 4 Epoxy (EP) coatings still show excellent corrosion resistance after 300h uv irradiation, have excellent ageing resistance, and two time constants are observed, which indicate that MOFs form a protective layer at the coating/metal interface. And NH 2 -MIL-101@b-C 3 N 4 the/EP coating exhibits lower corrosion resistance, which can be attributed to the excessive surface defects and undersize of the acid-stripped carbon nitride nanosheets, reducing themBarrier properties, while the MOFs are difficult to load to their surface. For pure EP coatings, the lowest resistance values and single time constants were exhibited, indicating low aging resistance and severe degradation of barrier properties.
FIG. 10 Bode diagram shows NH 2 -MIL-125@g-C 3 N 4 Epoxy (EP) coatings still show excellent corrosion resistance after 300h uv irradiation, have excellent ageing resistance, and two time constants are observed, which indicate that MOFs form a protective layer at the coating/metal interface. And NH 2 -MIL-125@b-C 3 N 4 the/EP coating exhibits lower corrosion resistance, which can be attributed to excessive surface defects and undersize of acid-stripped carbon nitride nanosheets, reducing their barrier properties, while MOFs are difficult to load onto their surface. For pure EP coatings, the lowest resistance values and single time constants were exhibited, indicating low aging resistance and severe degradation of barrier properties.
FIG. 11 Bode diagram shows MIL-100@ g-C 3 N 4 Epoxy (EP) coatings still show excellent corrosion resistance after 300h uv irradiation, have excellent ageing resistance, and two time constants are observed, which indicates that MOFs form a protective layer at the coating/metal interface. And MIL-100@ b-C 3 N 4 the/EP coating exhibits lower corrosion resistance, which can be attributed to excessive surface defects and undersize of acid-stripped carbon nitride nanosheets, reducing their barrier properties, while MOFs are difficult to load onto their surface. For pure EP coatings, the lowest resistance values and single time constants were exhibited, indicating low aging resistance and severe degradation of barrier properties.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. Preparation of g-C with large surface-to-diameter ratio 3 N 4 A method of nanoplatelets comprising:
fully grinding the carbon-nitrogen-rich small molecular compound and sodium chloride, and then treating the ground mixture at high temperature to obtain the large area-diameter ratio g-C with an in-plane highly ordered structure 3 N 4 Nanosheets.
2. The method according to claim 1, wherein the mass ratio of the carbon-nitrogen-rich small molecular compound to the sodium chloride is 1.
3. The method according to claim 2, wherein the mass ratio of the carbon-nitrogen-rich small molecular compound to the sodium chloride is 1.
4. The method according to claim 3, wherein the mass ratio of the carbon-nitrogen-rich small-molecular compound to the sodium chloride is 1.
5. The method according to any one of claims 1 to 4, wherein the carbon-nitrogen-rich small molecule compound is melamine, dicyandiamide, urea or thiourea.
6. The method of claim 1, wherein the elevated temperature is increased at a ramp rate of 5 to 10 ℃.
7. The method of claim 1 or 6, wherein the elevated temperature is from 500 ℃ to 600 ℃.
8. The method of claim 1, further comprising a process of washing to remove sodium chloride and dry the nanoplatelets after the treatment at the elevated temperature and cooling to room temperature.
9. The method of claim 8, wherein the washing is a deionized water washing.
10. The method of claim 8, wherein the drying is vacuum drying at 40-80 ℃ for 12-24 hours.
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