CN112010273B - Carbon nitride material with terminal group carbonylation and preparation method thereof - Google Patents

Carbon nitride material with terminal group carbonylation and preparation method thereof Download PDF

Info

Publication number
CN112010273B
CN112010273B CN201910468452.5A CN201910468452A CN112010273B CN 112010273 B CN112010273 B CN 112010273B CN 201910468452 A CN201910468452 A CN 201910468452A CN 112010273 B CN112010273 B CN 112010273B
Authority
CN
China
Prior art keywords
carbon nitride
temperature
peak
end group
attributed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910468452.5A
Other languages
Chinese (zh)
Other versions
CN112010273A (en
Inventor
王峰
苏凯艺
张超锋
黄志鹏
高著衍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201910468452.5A priority Critical patent/CN112010273B/en
Publication of CN112010273A publication Critical patent/CN112010273A/en
Application granted granted Critical
Publication of CN112010273B publication Critical patent/CN112010273B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Photovoltaic Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a preparation method of a carbon nitride nano flaky material subjected to end group carbonylation. G to C 3 N 4 Dispersing in amide solvent, putting in synthesis kettle, sealing, and introducing CO 2 Raising the temperature from room temperature to 60-200 ℃ for reaction, and keeping the temperature for 2-180 h. And after the reaction is finished, separating, washing and drying the precipitate to obtain the end group carbonylation carbon nitride nano flaky material. The material has aldehyde group at the end group, is of a layered structure, and has potential application in the fields of catalysis, organic photoelectric materials, sensors and the like.

Description

Carbon nitride material with terminal group carbonylation and preparation method thereof
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a preparation method of a carbon nitride nano flaky material subjected to end group carbonylation.
Background
Carbon and nitrogen elements widely exist in nature, and carbon nitride materials have important application in catalysis, electrodes, sensors and lithium battery electrode materials. A common compound for carbon nitride materials is carbon nitride (g-C) in the graphite phase 3 N 4 ) Of real g-C 3 N 4 Is a very complex system whose element composition is in addition to carbon and nitrogen elementsThere are many hydrogen or oxygen elements present. Compared with g-C 3 N 4 In some cases differently element doped or structurally modified g-C 3 N 4 Can show more excellent performance in the photocatalytic selective oxidation reaction.
g-C for doping and structurally modifying oxygen-containing functional groups with different oxygen elements 3 N 4 The synthesis of the material has the following aspects: california leaf, California, et al (application. Catal. B: environ, 2017,204, 335- 3 N 4 A material. The method needs to undergo high-temperature solid-phase reaction during synthesis. Xieli et al (adv. Mater.,2016,28, 6940-6945.) treat g-C with a strong acid for extended periods of time 3 N 4 A g-C containing C-O, C ═ O and COOH groups is obtained 3 N 4 . Wherein, the strong oxidizing ability of acid is utilized to oxidize carbon atoms on a carbon nitride skeleton to obtain carbon-oxygen unsaturated bonds. J.Zou et al (applied. Catal. B: environ, 2018,221, 9-16.) obtain oxygen-doped g-C by hydrothermal and high temperature solid phase reaction at high temperature 3 N 4 . Lotsch et al (adv. Energ. Mater.,2017,1602251) produced continuously using KSCN and HCl at g-C 3 N 4 The end group introduces an amide group.
Related researches find that the oxygen element is doped and the carbon-based g-C is introduced 3 N 4 The method has good advantages in selective oxidation reaction serving as photocatalysis, but the synthesis method is mostly solid-phase high-temperature reaction, or partial oxidation reduction at high-temperature hydrothermal process or partial oxidation of unsaturated carbon-nitrogen double bonds or carbon-nitrogen single bonds by using strong acid, because the position and the content of doping elements cannot be controlled generally, the obtained materials are mostly not pure, and the preparation of directionally distributed element-doped g-C is difficult 3 N 4 . According to previous literature reports (ChemSusChem,2015,8, 2066-2072.) in CO 2 Under the conditions of atmosphere and heating, the similar N, N-dimethylformamide molecule reacts with another amine molecule, and carbonyl is transferred from amide to another amine molecule to form dimethylamine and another amide molecule, namely, the conversion formylation reaction. And due to g-C 3 N 4 Containing about 15% of terminal amino groups (chem. Rev.,2016,116,7159- 3 N 4 The terminal amino group on the amino group is directionally modified.
The material structure determines the performance of the material, so that the development of a reliable and structure-controllable carbon nitride nano flaky material and a synthetic method thereof have important significance. Due to the unique structure of the material, the material can be potentially applied to the fields of catalysis, organic photoelectric materials, sensors and the like.
Disclosure of Invention
The invention provides a preparation method of end group carbonylation carbon nitride nano sheet material, which is prepared from the raw materials of g-C 3 N 4 The structure of the composite material is characterized in that the end group aldehyde group is directionally introduced on the basis of the structure, the composite material has the characteristics of good thermal stability, large specific surface area, layered structure on the crystal structure and the like, and can be applied to the fields of catalysis, organic photoelectric materials, sensors and the like.
The technical scheme of the invention is as follows: will contain g-C 3 N 4 The compound (B) is dispersed in an amide solution (N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide and the like), placed in a synthesis kettle, sealed and then introduced with 0.1-10 MPa of CO 2 Then raising the temperature to 60-200 ℃ at a heating rate of 1-20 ℃/min, and standing for 2-180 h. And after the reaction is finished, separating, washing and drying the precipitate to obtain the carbon nitride nano flaky material with the end group of aldehyde group. The carbon nitride material is directionally introduced in carbonyl groups, and the strong acid and high-temperature solid phase method reported in the prior literature is avoided. The preparation principle of the material is as follows: by reaction at CO 2 The catalytic conversion formylation reaction utilizes various amide organic matters and terminal carbonyl of carbon nitride to carry out conversion formylation reaction, and regulates and controls reaction time and reaction temperature to control the degree of conversion formylation and realize the introduction of aldehyde group on the terminal of the carbon nitride.
The choice of amide compound has an important influence on the synthesis of this material. Different amide compounds have different conversion formylation capacities at different concentrations and different temperatures, and have important influence on the terminal carbonylation of the synthesized material. Amide compoundsThe amide compound can be one or more of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-diisopropylformamide, N-dibutylformamide, N-diamylformamide and N, N-dihexylformamide, and the preferred amide compound is: one or more of N, N-dipropyl formamide, N-diisopropyl formamide, N-dibutyl formamide, N-diamyl formamide and N, N-dihexyl formamide, and the optimal amide compound is: one or two of N, N-dimethylformamide and N, N-diethylformamide. The amount of amide is suitably from 0.05 to 0.5mL (amide)/g (g-C) 3 N 4 ) The preferred amounts of amide are: 0.1 to 0.3mL (amide)/g (g-C) 3 N 4 ) The optimum amount of amide is 0.2-0.25 mL (amide)/g (g-C) 3 N 4 )。
Besides selecting the properly matched amide compound, the key point of material synthesis lies in reasonably adjusting the reaction temperature and CO during synthesis 2 Pressure, reaction time, temperature and time of incubation, etc. The suitable dispersion temperature is 10 ℃ to 50 ℃, the preferred mixing temperature is 20 ℃ to 40 ℃, and the most preferred mixing temperature is 30 ℃ to 35 ℃.
Suitable reaction times are: 1-180 h, and the preferable reaction time is as follows: 5 h-90 h, and the optimal reaction time is as follows: 24-72 h. Suitable standing reaction temperatures are: 60-200 ℃, and the preferable standing reaction temperature is as follows: 90-180 ℃, and the optimal standing reaction temperature is as follows: 120-150 ℃. Suitable rate of temperature rise: 1-20 ℃/min, and the preferable heating rate is as follows: 5-18 ℃/min, the optimal temperature rise rate: 10 to 15 ℃/min. Suitable CO 2 Pressure: 0.1 to 10MPa, preferably CO 2 The pressure is as follows: 1-5 MPa, most preferably CO 2 The pressure is as follows: 3 to 4 MPa.
The invention relates to a carbon nitride nano sheet material with end group carbonylation and a preparation method thereof, and has the advantages that:
(1) avoiding the use of strong acidic reagents (e.g., sulfuric acid and hydrochloric acid);
(2) the synthesized material is directionally introduced with aldehyde group on the basis of carbon nitride, and has a layered structure on a crystal structure.
The two-dimensional nano flaky structure has aldehyde group, the preparation method is simple, and the synthesis process is easy to control. The obtained material can be used in catalysis, organic photoelectric materials, sensors and the like.
Drawings
Fig. 1 is a FT-IR spectrum of the carbon nitride nanosheet material prepared in example 1.
Fig. 2 is a transmission electron microscope image of the carbon nitride nanosheet material prepared in example 1.
FIG. 3 is g-C 3 N 4 And the activity difference of the carbon nitride nanosheet material prepared in example 17 in photocatalytic benzylamine oxidation.
Reaction conditions are as follows: 10mg of catalyst, 1mL of a 0.1mmol solution of benzylamine in acetonitrile, O 2 (1atm), reaction time 9h, reaction temperature 40 ℃, light wavelength 455nm, 6W LEDs.
The specific implementation mode is as follows:
in order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Example 1:
at 10 ℃ 0.1g of g-C 3 N 4 Dispersing in 50ml N, N-dimethyl formamide, sealing, introducing 10MPa CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 2:
0.1g of g-C is added at 20 DEG C 3 N 4 Dispersing in 50ml N, N-dimethyl formamide, sealing, introducing 10MPa CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is completed, the mixture is filteredAnd washing with deionized water and drying in vacuum to obtain the carbon nitride nano flaky material with the end group of aldehyde group. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 3:
0.1g of g-C is added at 30 DEG C 3 N 4 Dispersing in 50ml N, N-dimethyl formamide, sealing, introducing 10MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 1 ℃/min, and standing for 180 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to the stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 4:
0.1g of g-C is added at 35 DEG C 3 N 4 Dispersing in 50ml N, N-dimethyl formamide, sealing, introducing 10MPa CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The C1 s spectrum in XPS shows a peak at 287.8eV, and the peak is assigned to C ═ O, which indicates that the carbon nitride nano flaky material with the end group of aldehyde group is successfully prepared.
Example 5:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 50ml N, N-dimethyl formamide, sealing, and placing in a synthesis kettleIntroducing 10MPa of CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 6:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 30ml of N, N-diethylformamide, placing in a synthesis kettle, sealing, and introducing 10MPa CO by replacement 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The C1 s spectrum in XPS shows a peak at 287.8eV, and the peak is assigned to C ═ O, which indicates that the carbon nitride nano flaky material with the end group of aldehyde group is successfully prepared.
Example 7:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 10ml N, N-diethylformamide, placing in a synthesis kettle, sealing, introducing 10MPa CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 8:
at 40 DEG CNext, 0.1g of g-C 3 N 4 Dispersing in 20ml of N, N-diethylformamide, placing in a synthesis kettle, sealing, and introducing 10MPa of CO for replacement 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 9:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-diethylformamide, putting in a synthesis kettle, sealing, introducing 10MPa CO for replacement 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The C1 s spectrum in XPS shows a peak at 287.8eV, and the peak is assigned to C ═ O, which indicates that the carbon nitride nano flaky material with the end group of aldehyde group is successfully prepared.
Example 10:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-dipropyl formamide, putting in synthetic reactor, sealing, and introducing 5MPa CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to the stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride with the end group of aldehyde group is successfully preparedA nano-platelet material.
Example 11:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 25ml N, N-dipropyl formamide, putting in synthetic reactor, sealing, and introducing 4MPa CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 12:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 25ml N, N-dipropyl formamide, putting in synthetic reactor, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 1 ℃/min, and standing for 180 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 13:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 25ml N, N-dipropyl formamide, putting in synthetic reactor, sealing, and introducing 1MPa CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 Absorption peak of (2) is attributed to stretching vibration of C ═ OAnd (6) moving. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 14:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-diisopropyl formamide, putting in synthetic kettle, sealing, introducing 0.1MPa CO 2 Raising the temperature to 200 ℃ at the heating rate of 1 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 15:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-diisopropyl formamide, putting in synthetic kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 180 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 16:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-diisopropyl formamide, putting in synthetic kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 18 ℃/min, and standing for 180 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. Obtained by observing and preparing through transmission electron microscope testThe carbon nitride material is a sheet structure. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 17:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-diisopropyl formamide, putting in synthetic kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 18:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 25ml of N, N-dibutyl propyl formamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO for replacement 2 Raising the temperature to 200 ℃ at a heating rate of 15 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 19:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml of N, N-dibutylformamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO for replacement 2 Raising the temperature to 200 ℃ at a heating rate of 10 ℃/min, and standing for 180 hours. After the synthesis is finished, filtering and deionized waterWashing and vacuum drying to obtain the carbon nitride nano flaky material with the end group of aldehyde group. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 20:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-dibutyl formamide, sealing, introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 5 ℃/min, and standing for 180 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 21:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml of N, N-dibutylformamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO for replacement 2 Raising the temperature to 60 ℃ at a temperature rise rate of 20 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 22:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-diamyl formamide, sealing in synthesizing kettle, and introducing 3MPa CO 2 Raising the temperature to 90 ℃ at a heating rate of 20 ℃/min, and standing for 180 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 23:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 25ml N, N-diamyl formamide, sealing in synthesizing kettle, and introducing 3MPa CO 2 Raising the temperature to 120 ℃ at a heating rate of 20 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 24:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-diamyl formamide, sealing in synthesizing kettle, and introducing 3MPa CO 2 Raising the temperature to 150 ℃ at a temperature rise rate of 20 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 25:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 25ml N, N-diamyl formamide, sealing in synthesizing kettle, and introducing 3MPa CO 2 Raising the temperature to 180 ℃ at a temperature rise rate of 20 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 26:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml of N, N-dihexylformamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 180 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 27:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 25ml of N, N-dihexylformamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 2 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 28:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml of N, N-dihexylformamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 5 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.
Example 29:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml of N, N-dihexylformamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 24 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The C1 s spectrum in XPS shows a peak at 287.8eV, and the peak is assigned to C ═ O, which indicates that the carbon nitride nano flaky material with the end group of aldehyde group is successfully prepared.
Example 30:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml of N, N-dihexylformamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 72 h. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By using FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. C1 s spectra in XPSThe peak is showed at 287.8eV, and the peak is assigned to C ═ O, which indicates that the carbon nitride nano sheet material with the end group of aldehyde group is successfully prepared.
Example 31:
0.1g of g-C is added at 40 DEG C 3 N 4 Dispersing in 25ml N, N-dihexylformamide, placing in a synthesis kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 90 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The C1 s spectrum in XPS shows a peak at 287.8eV, and the peak is assigned to C ═ O, which indicates that the carbon nitride nano flaky material with the end group of aldehyde group is successfully prepared.
Example 32:
at 40 ℃ 0.1g of g-C 3 N 4 Dispersing in 25ml of N, N-dihexylformamide, putting in a synthesis kettle, sealing, and introducing 3MPa CO 2 Raising the temperature to 200 ℃ at a heating rate of 20 ℃/min, and standing for 180 hours. After the synthesis is finished, the carbon nitride nano flaky material with the end group of aldehyde group is obtained by filtering, washing with deionized water and drying in vacuum. And (3) observing the prepared carbon nitride material to be in a sheet structure by using a transmission electron microscope test. By FT-IR test, found at 1700cm -1 The absorption peak of (2) is attributed to stretching vibration of C ═ O. The spectrum of C1 s in XPS shows a peak at 287.8eV, and the peak is attributed to C ═ O, which indicates that the carbon nitride nanosheet material with the end group being aldehyde group is successfully prepared.

Claims (8)

1. The application of the carbon nitride nano flaky material subjected to end group carbonylation in photocatalytic benzylamine oxidation is characterized in that:
g to C 3 N 4 Dispersing in an amide solvent, stirring, transferring, placing in a synthesis kettle, sealing, and introducing 0.1-10 MPa CO 2 (ii) a Then from the dispersing temperature to 1-20 DEG C o The temperature rise rate of C/min is increased to 60-200 o C reaction temperature, holding 2180 h; after the reaction is finished, washing and separating, washing and drying the precipitate by deionized water to obtain the carbon nitride nano material; the amide solvent is one or more than two of N, N-dimethylformamide, N-diethylformamide, N-dipropylformamide, N-diisopropylformamide, N-dibutylformamide, N-dipentylformamide and N, N-dihexylformamide; reaction conditions are as follows: 10mg of catalyst, 1mL of a 0.1mmol solution of benzylamine in acetonitrile, O 2 1atm, reaction time 9h, reaction temperature 40 o C, 6W LEDs with the illumination wavelength of 455 nm.
2. Use according to claim 1, characterized in that:
g to C 3 N 4 The temperature of dispersion in the amide solvent was 10 deg.C o C ~ 50 o C。
3. Use according to claim 2, characterized in that:
g to C 3 N 4 The temperature of dispersion in the amide solvent was 20 deg.C o C ~ 40 o C。
4. Use according to claim 3, characterized in that:
g to C 3 N 4 The temperature of dispersion in the amide solvent was 30 deg.C o C ~ 35 o C。
5. Use according to claim 1, characterized in that:
the dosage of the amide is 0.05-0.5 mL of amide/mg g-C 3 N 4 。
6. Use according to claim 1, characterized in that:
CO 2 the pressure is as follows: 1 to 5 MPa.
7. Use according to claim 6, characterized in that:
CO 2 the pressure of (A) is 3-4 MPa.
8. Use according to claim 1 or 2, characterized in that:
the temperature rise rate from the dispersion temperature to the reaction temperature is 10-15 o C/min, and the heat preservation time is 24-72 h.
CN201910468452.5A 2019-05-31 2019-05-31 Carbon nitride material with terminal group carbonylation and preparation method thereof Active CN112010273B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910468452.5A CN112010273B (en) 2019-05-31 2019-05-31 Carbon nitride material with terminal group carbonylation and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910468452.5A CN112010273B (en) 2019-05-31 2019-05-31 Carbon nitride material with terminal group carbonylation and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112010273A CN112010273A (en) 2020-12-01
CN112010273B true CN112010273B (en) 2022-09-20

Family

ID=73501563

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910468452.5A Active CN112010273B (en) 2019-05-31 2019-05-31 Carbon nitride material with terminal group carbonylation and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112010273B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114100665B (en) * 2021-12-06 2024-03-29 合肥工业大学 Preparation method and application of carbonyl functionalized graphite phase carbon nitride

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106475126A (en) * 2016-08-30 2017-03-08 武汉理工大学 A kind of graphite phase carbon nitride photochemical catalyst with nanobelt shape structure

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106475126A (en) * 2016-08-30 2017-03-08 武汉理工大学 A kind of graphite phase carbon nitride photochemical catalyst with nanobelt shape structure

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
C-N and N-H Bond Metathesis Reactions Mediated by Carbon Dioxide;Yehong Wang等;《ChemSusChem》;20150603;第8卷;conclusion部分和图8 *
Enhanced Singlet Oxygen Generation in Oxidized Graphitic Carbon Nitride for Organic Synthesis;Hui Wang等;《Advanced Materials》;20160606;第28卷;experimental section部分第1-2段、第6941页左栏第5-11行、右栏3-7行、图1-c和图1-d *
g-C3N4基光催化剂的制备和应用;马小帅等;《有色金属科学与工程》;20180630;第9卷(第3期);第42-52页 *
Graphitic Carbon Nitride(g-C3N4)-Based Photocatalysts for Artifical Photosynthesis and Environmental Remediation: Are we a Step Closer to Achieving Sustainability?;Wee-Jun Ong等;《Chemical Reviews》;20160520;第116卷;第7159-7329页 *
石墨相氮化碳的化学合成及应用;张金水等;《物理化学学报》;20130930;第29卷(第9期);第1865-1876页 *
超薄石墨相氮化碳纳米片的构建及其光催化作用;陈艳等;《无机化学学报》;20171231;第33卷(第12期);第2255-2261页 *

Also Published As

Publication number Publication date
CN112010273A (en) 2020-12-01

Similar Documents

Publication Publication Date Title
Han et al. Graphene/graphitic carbon nitride hybrids for catalysis
CN104447209A (en) Method for preparing cyclohexanol by catalyzing by base metal catalyst
CN110743592B (en) Perovskite photocatalyst and preparation method and application thereof
WO2021008196A1 (en) Catalyst for electrocatalytic carbon dioxide reduction and preparation method thereof
CN114367299B (en) Graphite phase carbon nitride photocatalyst for photocatalytic hydrogen production and preparation method thereof
CN1310044A (en) Cds photocatalyst for producing hydrogen, its producing process and process for producing hydrogen using the same catalyst
CN111036243B (en) Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof
CN107935816B (en) Method for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol
CN108666584A (en) A kind of Co-N-C/ carbon nano-tube catalysts and its preparation method and application
CN106986755B (en) Method for preparing p-hydroxybenzaldehyde by photocatalysis
CN112010273B (en) Carbon nitride material with terminal group carbonylation and preparation method thereof
Longobardo et al. Tailored amorphization of graphitic carbon nitride triggers superior photocatalytic C–C coupling towards the synthesis of perfluoroalkyl derivatives
CN103143381B (en) Carbon nitride material immobilized heteropolyacid catalyst and olefin epoxy synthesizing method
CN111822029A (en) Bi4V2O11/g-C3N4Heterojunction photocatalyst and preparation method and application thereof
CN112657530A (en) Non-noble metal immobilized nitrogen-doped carbon nanotube catalyst, and preparation method and application thereof
CN111875546B (en) Echinoid cobalt-based photocatalyst for converting CO2Application of synthesizing benzimidazolone compounds
Prajapati et al. Unravelling the redox behaviour of a carbon nitride polymer-based ternary heterostructure for CO 2 photoreduction promoted by amine coupling
CN108658059B (en) Preparation method of tungsten trioxide/nitrogen-doped graphene compound
CN111318296B (en) Preparation method and application of supported cobalt/carbon nanotube material derived from zeolite imidazole framework material
CN112547124B (en) Selective hydrogenation catalyst for halogenated nitrobenzene, preparation method thereof and method for catalyzing selective hydrogenation of halogenated nitrobenzene
CN107555413B (en) Preparation method of nitrogen-doped ordered mesoporous carbon with adjustable nitrogen content
CN114849789B (en) Preparation method and application of MIL-125 supported 1T-phase molybdenum sulfide composite photocatalyst
CN109225297B (en) Composite catalyst QDs-SISCN and preparation method and application thereof
CN113398968A (en) MOF-derived TiO2Porous g-C3N4Composite photocatalyst and preparation method and application thereof
CN107866249B (en) Molybdenum carbide catalyst for preparing nerol and geraniol by hydrogenating citral

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant