Chain cyano carbodiimide as well as preparation method and application thereof
By preparing chain cyanocarbodiimide (C2N3H) as active precursors, the problem of synthesis of two-dimensional layered CxNy materials at high temperature in the prior art is solved, and the precursors for efficient preparation of CxNy layered materials under conventional conditions is realized, which reduces the difficulty of synthesis and provides a new way for the design of new functional materials.
Patent Information
- Application Number
- CN202510594992.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-09
- Publication Date
- 2025-09-02
AI Technical Summary
The synthesis of two-dimensional layered CxNy materials in the prior art requires a higher reaction temperature, which leads to increased synthesis difficulty, and it is urgent to develop new precursors with high reactivity.
A chain-shaped cyanocarbodiimide (C2N3H) is used as the active precursor and is prepared under conventional conditions by bombarding graphite phase nitriding carbon powder by high-energy particles to form a V-shaped chain structure with cyano and carbodiimide group bifunctional groups.
The precursor of CxNy layered material with high chemical reactivity was successfully prepared under conventional conditions, reducing the difficulty of synthesis and providing a new growth mechanism for the design of new two-dimensional CxNy-based functional materials.
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Figure CN120574151A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the fields of photoelectric materials, organic synthesis catalysts and high-energy material precursor preparation, and relates to a chain cyanocarbodiimide, a preparation method and application thereof. Background Art
[0002] 2D layered C x N y The material, formed by carbon and nitrogen atoms linked in varying chemical ratios, possesses a unique graphene-like layered structure. This layered structure gives the material a high specific surface area and abundant surface active sites, which facilitate adsorption and catalytic reactions. The adjustable C / N ratio and doping optimize electronic properties, resulting in excellent visible light responsiveness. The tunable interlayer spacing and excellent conductivity make it suitable for use as an electrode material in lithium-ion batteries and supercapacitors, enhancing charge storage efficiency. Therefore, this material exhibits significant potential in photocatalytic energy conversion (such as water splitting to produce hydrogen and CO2 reduction), environmental pollutant degradation, high-efficiency energy storage devices, and biomedical applications.
[0003] Journal of the American Chemical Society, 2001, 123, (32): 7788-7796. Using a solid-phase reaction method, melamine and cyanuric chloride were used as precursors. The reaction was conducted at 1.0-1.5 GPa and 500-550°C to prepare a two-dimensional layered C6N9H3 catalyst with regular C3N3 voids inside. Chloride ions fill the larger voids in the structure, and the number of chloride ions in the framework is equal to the number of protonated nitrogen atoms, achieving charge balance in the system. AngewandteChemie International Edition, 2012, 51, (47): 11814-11818. Using a solvent-thermal synthesis method, melamine and cyanuric chloride were used as precursors and acetonitrile was used as the solvent. A rod-shaped nano-g-C3N4 material with catalytic performance in the decomposition of p-chlorophenol was successfully prepared. Applied Catalysis B: Environmental, 2020, 274, 119116. Using thermal polymerization at 550 ° C, malondiamide (MLDD) and urea molecules as precursors, carbon bridge modified g-C3N4 nanosheets were successfully prepared, which improved the conjugated system of graphite phase carbon nitride. The sample showed excellent photocatalytic performance in pollutant degradation and catalytic hydrogen production. In summary, the current synthesis of two-dimensional layered C x N y Most of the precursors used in the materials require a relatively high reaction temperature for synthesis. Therefore, it is urgent to develop new precursors with high reactivity to reduce the difficulty of synthesis and provide a new type of two-dimensional C x N yThe design of basic functional materials provides new precursors and growth mechanisms. Summary of the Invention
[0004] The present invention aims to synthesize two-dimensional layered C x N y Most of the precursors used need to undergo a relatively high reaction temperature, and provide a chain cyanocarbodiimide, a preparation method and an application thereof.
[0005] The technical solution adopted by the present invention is:
[0006] A chain cyanocarbodiimide, which is a C2N3H atomic cluster;
[0007] Its chemical formula is N≡CN=C=NH;
[0008] It has a bifunctional structure of cyano and carbodiimide groups.
[0009] Specifically, the C2N3H atomic cluster is a V-shaped chain structure, with a cyano group on one side and a carbodiimide group on the other side.
[0010] Specifically, its spatial structure is:
[0011]
[0012] The method for preparing any of the chain cyanocarbodiimides of the present invention comprises the following steps:
[0013] a. The graphite phase carbon nitride powder is pressed into a tablet having a diameter of 5 to 15 mm and a thickness of 3 to 10 mm, and then the tablet is placed in the source chamber;
[0014] b. Seal the source chamber and pump the vacuum degree to 10 -4 ~10 -6 Pa, uses high-energy particles to bombard the tablets and introduces inert gas with a flow rate of 80 to 200 ml / min; the clusters produced are C2N3H atomic clusters.
[0015] Optionally, the high-energy particle bombardment is laser sputtering;
[0016] The laser used in the laser sputtering has a wavelength of 266 to 1064 nm, an energy of 5 to 20 mJ / pulse, and a repetition frequency of 5 to 20 Hz.
[0017] Optionally, the high-energy particle bombardment is arc discharge;
[0018] The arc discharge current is 5000A, and the discharge time is 5 microseconds.
[0019] Optionally, the high-energy particle bombardment is magnetron sputtering;
[0020] The voltage of the magnetron sputtering is 240 V, and the argon gas pressure is 10 mTorr.
[0021] Optionally, the inert gas is nitrogen, helium or argon.
[0022] Specifically, it includes:
[0023] 0.6-2.0 g of graphite phase carbon nitride powder is pressed into a tablet having a diameter of 10 mm and a thickness of 8-11 mm;
[0024] At a vacuum degree of 4×10 -6 ~10 -6 Pa, using high-energy particles to bombard the tablets;
[0025] The high-energy particle bombardment is laser sputtering, the laser wavelength is 532nm, the energy is 9-13mJ / pulse, and the repetition frequency is 10Hz;
[0026] Or the high-energy particle bombardment is arc discharge with a current of 5000A and a discharge time of 5 microseconds;
[0027] Or the high-energy particle bombardment is magnetron sputtering, the voltage is 240V, and the argon gas is 10mTorr;
[0028] Inert gas is introduced with a flow rate of 90 to 120 ml / min, and the generated clusters are C2N3H atomic clusters.
[0029] Any of the chain cyanocarbodiimides of the present invention is used as an active precursor to construct C x N y Application of layered materials.
[0030] Advantages of the present invention:
[0031] The present invention is the first to prepare the structure C under conventional conditions x N y A new active cluster precursor of layered materials, cyanocarbodiimide (C2N3H), has the structure Figure 2 As shown in Figure 1, the precursor has a V-shaped chain structure with a cyano group on the left and a carbodiimide group on the right, which has high chemical reactivity. Currently, there is no report in the literature on the preparation of chain cyanocarbodiimide (C2N3H) under conventional conditions. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the following detailed description, they are used to explain the present invention but do not constitute a limitation of the present invention. In the accompanying drawings:
[0033] Figure 1It is obtained by laser sputtering [(C2N3) n H n-1 ] - (n=1-4) cluster mass spectra;
[0034] Figure 2 Yes [(C2N3) n H n-1 ] - (n=1-4) Cluster lowest energy structure diagram;
[0035] Figure 3 are the electrostatic potential (ESP) and average local ionization energy (ALIE) of 1HA ((a) and (b)) and 1A ((c) and (d)) on the molecular surface;
[0036] Figure 4 It is the 3A cluster formation path and reaction activation energy diagram;
[0037] Figure 5 It is the 4A cluster formation path and reaction activation energy diagram;
[0038] Figure 6 These are two possible generation paths of the 5A cluster. DETAILED DESCRIPTION
[0039] The present invention is further described in detail below with reference to the examples.
[0040] The following are examples of implementation provided by the inventors. It should be noted that these embodiments are preferred examples and are primarily used to understand the present invention, but the present invention is not limited to these embodiments. It should be noted that any process not specifically described below is readily understood or understood by those skilled in the art with reference to the prior art. Reagents or instruments used without manufacturer indicated are deemed to be commercially available conventional products.
[0041] The chain cyanocarbodiimide of the present invention has a chemical formula of N≡CN=C=NH and has a unique bifunctional structure of cyano and carbodiimide. The preparation steps are as follows: pressing graphite phase carbon nitride powder into a disc sample and placing it in a source chamber; turning on the vacuum system, evacuating the chamber to vacuum, turning on the high-energy particle bombardment device, bombarding the graphite phase carbon nitride pellet with high-energy particles to induce CN bond breakage and recombination, and introducing high-purity nitrogen as carrier gas and cooling gas; using time-of-flight mass spectrometry to detect the product, confirming the generation of C2N3H atomic clusters; finally, through DFT calculation, it is determined that it has a unique bifunctional structure of cyano and carbodiimide, has high chemical activity and electron delocalization characteristics, and can be used to construct optoelectronic materials, organic synthesis catalysts and high-energy material precursors. The present invention has discovered for the first time a method for constructing C x N yCyanocarbodiimide (C2N3H), a novel active precursor of layered materials, has a unique bifunctional structure and is a new type of two-dimensional C x N y The design of basic functional materials provides new precursors and growth mechanisms.
[0042] The idea of the present invention is to use a laser sputtering device to sputter a graphite carbon nitride substrate under vacuum conditions with the help of pulsed laser, and emit various particles through evaporation and cutting of chemical bonds to generate plasma. Then, high-pressure gas is injected in the form of pulses under adiabatic conditions, and the plasma formed by molecular collision, expansion, and rapid cooling is formed to form a C x N y Novel active cluster precursors for layered materials.
[0043] Time-of-flight mass spectrometry (TOF-MS) analysis confirmed the formation of C2N3H atomic clusters. Finally, density functional theory (DFT) calculations confirmed that it has a unique bifunctional structure with cyano and carbodiimide groups, as shown in the figure below:
[0044]
[0045] The main steps of the preparation method of the chain cyanocarbodiimide of the present invention are as follows:
[0046] Graphite-phase carbon nitride powder was pressed into a disc-shaped sample and placed in the source chamber; the vacuum system was turned on, the cavity was evacuated to a vacuum, and the high-energy particle bombardment device was turned on. The graphite-phase carbon nitride disc was bombarded with high-energy particles to induce the breakage and recombination of CN bonds, and high-purity nitrogen was introduced as carrier gas and cooling gas; the product was detected by time-of-flight mass spectrometry, confirming the generation of C2N3H atomic clusters; finally, DFT calculations determined that it had a unique bifunctional structure with cyano and carbodiimide groups, with high chemical activity and electron delocalization characteristics.
[0047] The specific steps are as follows:
[0048] 1.3 g of analytically pure graphite phase carbon nitride powder was pressed into a disc sample with a diameter of 10 mm and a thickness of about 9 mm. The sample was then placed in the source chamber. The vacuum system was turned on and the vacuum degree of the chamber was pumped to 10 -6 Pa, turned on the high-energy particle bombardment device, and bombarded the graphite phase carbon nitride pressed sheet with a high-energy laser with a wavelength of 532nm, an energy of 13mJ / pulse, and a repetition frequency of 10Hz, and introduced high-purity nitrogen as carrier gas and cooling gas, with a nitrogen flow rate of 100ml / min; time-of-flight mass spectrometer (TOF-MS) detection and analysis confirmed the generation of C2N3H atomic clusters; finally, density functional theory (DFT) calculations determined that it was a unique bifunctional structure with cyano and carbodiimide groups.
[0049] Example 1:
[0050] 1.3 g of analytically pure graphite phase carbon nitride powder was pressed into a disc sample with a diameter of 10 mm and a thickness of about 9 mm. The sample was then placed in the source chamber. The vacuum system was turned on and the vacuum degree of the chamber was pumped to 10 -6 Pa, turned on the high-energy particle bombardment device, and bombarded the graphite phase carbon nitride pressed sheet with a high-energy laser with a wavelength of 532nm, an energy of 13mJ / pulse, and a repetition frequency of 10Hz, and introduced high-purity nitrogen as carrier gas and cooling gas, with a nitrogen flow rate of 100ml / min; time-of-flight mass spectrometer (TOF-MS) detection and analysis confirmed the generation of C2N3H atomic clusters; finally, density functional theory (DFT) calculations determined that it was a unique bifunctional structure with cyano and carbodiimide groups.
[0051] Table 1
[0052]
[0053] The mass spectra of the generated anion clusters are shown in Figure 2. Figure 1 As shown, a series with a mass difference of 67 [(C2N3) n H n-1 ] - (n=1-4) clusters, indicating that this series of clusters is formed by C2N3 - Gradually combined with C2N3H growth formation.
[0054] Molculs and Gaussian programs were used to search the structures of the clusters found, and the lowest energy [(C2N3) n H n-1 ] - (n=1-4) cluster structure such as Figure 2 Combined with the data in Table 1, it can be seen that C2N3H(1A) is a V-shaped chain structure with a cyano group on the left and a carbodiimide group on the right, where the carbodiimide group is a unique structure with three centers and four electrons.
[0055] In order to further explore the distribution of reaction sites during the structural evolution process, electrostatic potential (ESP) and average local ionization energy (ALIE) were used to predict the reaction active sites of 1A and 2A. Figure 3Detailed information on ESP and ALIE is presented. The electrostatic potential of the ESP surface of 1A gradually changes from negative to positive from left to right, with the alternating arrangement of CN atoms forming local areas of alternating positive and negative potential. The most negative electrostatic potential is observed in the nitrogen atom region at the far left of the structure, while the most positive potential is observed at the hydrogen atom on the right. The ESP surface of 2A exhibits an overall negative potential characteristic, with a global minimum around the middle nitrogen atom and a wide negative potential region, indicating significant electron delocalization in this region. This complementary electrostatic distribution promotes electrostatic attraction between the N atom connected to the H atom in 1A and the C atom connected to the N atom in 2A, forming a stable bond through a synergistic electrophilic-nucleophilic effect.
[0056] Figure 4 The transition state and activation energy of the reaction from 1A and 2A to 3A are shown. In the transition state, the connection site between the two precursors is on the three-center four-electron carbodiimide group.
[0057] Figure 5 Schematic diagram of the distribution and combination of two 1A and 2A to form cyclic 4A and the reaction activation energy. The connection site of the three fragments in 4A is also on the three-center four-electron carbodiimide group;
[0058] Figure 6 Two possible pathways for the formation of 5A structures are shown: the first pathway uses 3A as the structural framework and self-assembles two 1A molecules ( Figure 6 (a)); the second generation pathway uses 4A as the core skeleton and combines it with a 1A molecule to construct ( Figure 6 (b), 3A and 4A are marked with dark red dashed boxes, and 1A is marked with a light red dashed box. In summary, the V-shaped chain precursor cyanocarbodiimide (C2N3H), with a cyano group on the left and a carbodiimide group on the right, has high chemical reactivity.
[0059] Example 2:
[0060] 0.9 g of analytically pure graphite phase carbon nitride powder was pressed into a disc sample with a diameter of 10 mm and a thickness of about 11 mm. The sample was then placed in the source chamber. The vacuum system was turned on and the vacuum degree of the chamber was pumped to 2×10 -6 Pa, turned on the high-energy particle bombardment device, and bombarded the graphite phase carbon nitride pressed sheet with a high-energy laser with a wavelength of 532nm, an energy of 10mJ / pulse, and a repetition frequency of 10Hz, and introduced high-purity nitrogen as carrier gas and cooling gas, with a nitrogen flow rate of 90ml / min; time-of-flight mass spectrometer (TOF-MS) detection and analysis confirmed the generation of C2N3H atomic clusters.
[0061] Example 3:
[0062] 0.6 g of analytically pure graphite phase carbon nitride powder was pressed into a disc sample with a diameter of 10 mm and a thickness of about 8 mm. The sample was then placed in the source chamber. The vacuum system was turned on and the vacuum degree of the chamber was pumped to 4×10 -6 Pa, turned on the high-energy particle bombardment device, and bombarded the graphite phase carbon nitride pressed sheet with a high-energy laser with a wavelength of 532nm, an energy of 9mJ / pulse, and a repetition frequency of 10Hz, and introduced high-purity argon as carrier gas and cooling gas, with an argon flow rate of 90ml / min; time-of-flight mass spectrometer (TOF-MS) detection and analysis confirmed the generation of C2N3H atomic clusters.
[0063] Example 4:
[0064] 2.0 g of analytically pure graphite phase carbon nitride powder was pressed into a disc sample with a diameter of 10 mm and a thickness of about 18 mm. The sample was then placed in the source chamber. The vacuum system was turned on and the vacuum degree of the chamber was pumped to 4×10 -6 Pa, turned on the magnetron sputtering device, voltage 240V, argon 10mTorr, the electrons generated by low-voltage discharge collided with argon atoms to ionize argon positive ions, which bombarded the graphite phase carbon nitride pressed sheets, and introduced high-purity nitrogen as carrier gas and cooling gas, with a nitrogen flow rate of 90ml / min; time-of-flight mass spectrometer (TOF-MS) detection and analysis confirmed the generation of C2N3H atomic clusters.
[0065] Example 5:
[0066] 0.7 g of analytically pure graphite phase carbon nitride powder was pressed into a disc sample with a diameter of 10 mm and a thickness of about 9 mm. The sample was then placed in the source chamber. The vacuum system was turned on and the vacuum degree of the chamber was pumped to 1.5×10 -6 Pa, turned on the arc discharge device, with a current of 5000A and a discharge time of 5 microseconds, acting on the graphite phase carbon nitride pressed sheet, and introduced high-purity helium as carrier gas and cooling gas, with a helium flow rate of 120ml / min; time-of-flight mass spectrometer (TOF-MS) detection and analysis confirmed the generation of C2N3H atomic clusters.
[0067] The above are only specific embodiments of the present invention, but the present invention is not limited to the above embodiments. Without departing from the design concept and principle of the present invention, various modifications, improvements and changes of the present invention should be included in the scope of protection of the present invention.
Claims
1. A chain cyanocarbodiimide, characterized in that It is a C2N3H atomic cluster; Its chemical formula is N≡CN=C=NH; It has a bifunctional structure of cyano and carbodiimide groups.
2. The chain cyanocarbodiimide according to claim 1, characterized in that The C2N3H atomic cluster is a V-shaped chain structure, with a cyano group on one side and a carbodiimide group on the other side.
3. The chain cyanocarbodiimide according to claim 1 or 2, characterized in that Its spatial structure is:
4. The method for preparing the chain cyanocarbodiimide according to any one of claims 1 to 3, characterized in that: The following steps are involved: a. The graphite phase carbon nitride powder is pressed into a tablet having a diameter of 5 to 15 mm and a thickness of 3 to 10 mm, and then the tablet is placed in the source chamber; b. Seal the source chamber and pump the vacuum degree to 10 -4 ~10 -6 Pa, uses high-energy particles to bombard the tablets and introduces inert gas with a flow rate of 80 to 200 ml / min; the clusters produced are C2N3H atomic clusters.
5. The method for preparing the chain cyanocarbodiimide according to claim 4, wherein: The high-energy particle bombardment is laser sputtering; The laser used in the laser sputtering has a wavelength of 266 to 1064 nm, an energy of 5 to 20 mJ / pulse, and a repetition frequency of 5 to 20 Hz.
6. The method for preparing the chain cyanocarbodiimide according to claim 4, wherein: The high-energy particle bombardment is arc discharge; The arc discharge current is 5000A, and the discharge time is 5 microseconds.
7. The method for preparing the chain cyanocarbodiimide according to claim 4, wherein: The high-energy particle bombardment is magnetron sputtering; The voltage of the magnetron sputtering is 240 V, and the argon gas pressure is 10 mTorr.
8. The method for preparing the chain cyanocarbodiimide according to claim 4, wherein: The inert gas is nitrogen, helium or argon.
9. The method for preparing the chain cyanocarbodiimide according to claim 4, wherein: Specifically include: 0.6-2.0 g of graphite phase carbon nitride powder is pressed into a tablet having a diameter of 10 mm and a thickness of 8-11 mm; At a vacuum degree of 4×10 -6 ~10 -6 Pa, using high-energy particles to bombard the tablets; The high-energy particle bombardment is laser sputtering, the laser wavelength is 532nm, the energy is 9-13mJ / pulse, and the repetition frequency is 10Hz; Or the high-energy particle bombardment is arc discharge with a current of 5000A and a discharge time of 5 microseconds; Or the high-energy particle bombardment is magnetron sputtering, the voltage is 240V, and the argon gas is 10mTorr; Inert gas is introduced with a flow rate of 90 to 120 ml / min, and the generated clusters are C2N3H atomic clusters.
10. The chain cyanocarbodiimide according to any one of claims 1 to 3 is used as an active precursor to construct C x N y Application of layered materials.