CN111439732B - C with good visible light response 6 N 7 Carbon nitride material and preparation method and application thereof - Google Patents
C with good visible light response 6 N 7 Carbon nitride material and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000004298 light response Effects 0.000 title abstract description 9
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
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- -1 oxalyl diamine Chemical class 0.000 claims abstract description 14
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940126062 Compound A Drugs 0.000 claims abstract description 11
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- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 230000015556 catabolic process Effects 0.000 claims description 15
- 238000006731 degradation reaction Methods 0.000 claims description 15
- YBQZXXMEJHZYMB-UHFFFAOYSA-N 1,2-diphenylhydrazine Chemical compound C=1C=CC=CC=1NNC1=CC=CC=C1 YBQZXXMEJHZYMB-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 4
- 229940012189 methyl orange Drugs 0.000 claims description 4
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- RGPBQGGBWIMGMA-BJMVGYQFSA-N 5-[(e)-[5-(4-bromophenyl)-6-hydroxy-3,6-dihydro-1,3,4-oxadiazin-2-ylidene]methyl]-1h-pyrimidine-2,4-dione Chemical compound OC1O\C(=C\C=2C(NC(=O)NC=2)=O)NN=C1C1=CC=C(Br)C=C1 RGPBQGGBWIMGMA-BJMVGYQFSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- APLNAFMUEHKRLM-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(3,4,6,7-tetrahydroimidazo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)N=CN2 APLNAFMUEHKRLM-UHFFFAOYSA-N 0.000 description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 3
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ULWOEWXTMNRFGW-UHFFFAOYSA-N n-anilino-n-phenylhydroxylamine Chemical compound C=1C=CC=CC=1N(O)NC1=CC=CC=C1 ULWOEWXTMNRFGW-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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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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Abstract
C with good visible light response 6 N 7 A carbon nitride material, a preparation method and application thereof, belonging to the technical field of photocatalytic materials. Solves the problem that the prior art does not have C 6 N 7 A method for producing a carbon nitride material having a structure. C of the invention 6 N 7 The preparation method of the carbon nitride material comprises the following steps: uniformly mixing the compound A and the compound B according to the mass ratio of (1-3): 1, reacting the obtained mixture for more than 1h at 425-700 ℃ in the air or inert atmosphere, and cooling to obtain C 6 N 7 The carbon nitride material comprises a compound A and a compound B, wherein the compound A is one or more of urea, cyanamide and thiourea, and the compound B is one or more of oxalyl diamine and oxalic acid. The C is 6 N 7 The preparation method of the carbon nitride material is simple, low in cost and convenient for large-scale production, and the prepared C 6 N 7 The carbon nitride material has a porous layered structure, stable physical and chemical properties, good conductivity, good visible light response and high photocatalytic activity.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a C with good visible light response 6 N 7 A carbon nitride material, a preparation method and application thereof.
Background
Graphite phase carbon nitride (g-C) 3 N 4 ) Has the advantages of low price, no toxicity, stable physical and chemical properties, relatively high photocatalytic activity and the like, and is an ideal photocatalyst. Has wide application in the aspects of photocatalytic hydrogen production, oxygen production, carbon dioxide reduction, catalytic organic reaction, sewage treatment and environmental protection.
Conventional g-C 3 N 4 The forbidden band width is about 2.88eV, only visible light with the wavelength less than or equal to 460nm can be absorbed, and the specific surface area is low, the photogenerated carriers are quickly compounded, and the conductivity is poor, thereby limiting the g-C to a certain extent 3 N 4 The practical application of (1). For this purpose, a series of methods, for example: morphology, structure regulation, doping or covalent modification, composite construction of heterojunctions with other semiconductor materials, and the like are reported successively to improve g-C 3 N 4 Photocatalytic activity of (1). But receive g-C 3 N 4 Sp in the structure itself 3 The limitation of N connection, the conjugation, visible light absorption and the transmission and separation of photogenerated carriers still have no breakthrough progress. Thus, the g-C is fundamentally changed 3 N 4 Knot (2)The development of a novel carbon nitride material with novel structure, high conjugation, good stability and wide visible light response range becomes an important challenge in the fields of photocatalysis and materials.
Recently, a series of heptazine ring-based carbon nitride materials with novel structures are predicted, a series of optimization and theoretical prediction are carried out on the structures and the physical and chemical properties of the materials, and the results show that the C of the heptazine ring directly connected through a C-C bond 6 N 7 Is a potentially excellent class of photocatalysts. Unfortunately, their synthesis has not been reported in the literature to date.
Disclosure of Invention
The invention aims to solve the problem that the prior art does not have C 6 N 7 The technical problem of the preparation method of the carbon nitride material with the structure is to provide C with good visible light response 6 N 7 A carbon nitride material, a preparation method and application thereof.
C of the invention 6 N 7 A method for preparing a carbon nitride material, comprising the steps of:
step one, uniformly mixing a compound A and a compound B according to the mass ratio (1-3): 1 to obtain a mixture;
the compound A is one or more of urea, cyanamide and thiourea;
the compound B is one or more of oxalyl diamine and oxalic acid;
step two, reacting the mixture obtained in the step one at the reaction temperature of 425-700 ℃ for more than 1h in air or inert atmosphere, and cooling to obtain C 6 N 7 A carbon nitride material.
Preferably, the mass ratio of the compound A to the compound B is 2.
Preferably, the reaction temperature is 450 to 650 ℃.
Preferably, the reaction time is 3h.
The temperature is preferably raised to the reaction temperature at a temperature raising rate of 20 ℃/min or less, and more preferably at a temperature raising rate of 5 ℃/min.
The present invention also provides the above-mentioned compound C 6 N 7 Preparation method of carbon nitride material C 6 N 7 A carbon nitride material.
The invention also provides the compound C 6 N 7 Use of carbon nitride materials as photocatalysts.
Preferably, C is 6 N 7 Carbon nitride material in photocatalysis hydrogen production, photocatalysis carbon dioxide reduction, photocatalysis nitrogen gas conversion into ammonia gas, photocatalysis diphenyl hydrazine oxidation, photocatalysis benzylamine oxidation, photocatalysis phenol degradation, photocatalysis halogenated phenol degradation, photocatalysis tetracycline degradation, photocatalysis methyl orange degradation, photocatalysis Cr 6+ Reduction, photocatalytic removal of NO 2 The use of (1).
Compared with the prior art, the invention has the following beneficial effects:
c of the invention 6 N 7 The carbon nitride material selects nitrogen-rich micromolecules containing single carbon atom, urea, mononitrile amine or thiourea, and oxalyl diamine or oxalic acid with C-C connection, and realizes C for the first time by simple high-temperature thermal polymerization 6 N 7 The visible light catalytic activity of the photocatalyst is systematically researched. The preparation method is simple, low in cost and convenient for large-scale production.
C of the invention 6 N 7 The carbon nitride material has a porous layered structure, stable physical and chemical properties, good conductivity, good visible light responsiveness and high photocatalytic activity.
C of the invention 6 N 7 The carbon nitride material is used for photocatalytic hydrogen production, photocatalytic carbon dioxide reduction, photocatalytic nitrogen conversion into ammonia gas, photocatalytic diphenyl hydrazine and benzylamine oxidation, photocatalytic phenol, halogenated phenol, tetracycline and methyl orange degradation, and photocatalytic Cr 6+ Reduction and photocatalytic removal of NO and NO 2 In addition, the method has great potential application value. Through test detection, under the irradiation of visible light, the photocatalytic hydrogen production amount of the carbon nitride material prepared by the method is 6 times that of carbon nitride prepared by taking urea as a precursor and 34 times that of carbon nitride prepared by taking melamine as the precursor; c prepared by the invention 6 N 7 Photocatalytic application of carbon nitride materialIn the reaction of oxidizing diphenyl hydrazine oxide and degrading halogenated phenol by photocatalysis, the conversion rate and the selectivity are close to 100 percent.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following disclosure are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
In FIG. 1, (a) and (b) are both C prepared in example 3 of the present invention 6 N 7 Scanning electron micrographs of carbon nitride, (C) and (d) are both C prepared in inventive example 3 6 N 7 Transmission electron micrographs of carbon nitride material;
FIG. 2 shows a graph of C prepared in example 3 of the present invention 6 N 7 Atomic force microscopy of carbon nitride;
FIG. 3 is the thickness of the solid line of FIG. 2 swept across the nanoplatelets;
FIG. 4 is C prepared according to example 3 of the present invention 6 N 7 X-ray energy spectrum analysis of carbon nitride;
FIG. 5 shows a graph of C prepared in example 3 of the present invention 6 N 7 X-ray powder diffraction pattern (XRD) of carbon nitride;
FIG. 6 shows a graph of C prepared in example 3 of the present invention 6 N 7 Solid carbon nuclear magnetic spectrum of carbon nitride;
FIG. 7 shows a graph of C prepared in example 3 of the present invention 6 N 7 Liquid carbon nuclear magnetic spectrum of carbon nitride;
in FIG. 8, (a) and (b) are each C prepared in example 3 of the present invention 6 N 7 X-ray photoelectron spectroscopy (XPS) fine spectra of C and N of carbon nitride;
FIG. 9 shows a graph of C prepared in example 3 of the present invention 6 N 7 Infrared spectroscopy of carbon nitride;
FIG. 10 shows a graph of C prepared in example 3 of the present invention 6 N 7 Raman spectrum of carbon nitride;
FIG. 11 shows example 3 of the present inventionPreparation of C 6 N 7 N of carbon nitride 2 Adsorption curve diagram;
in FIG. 12, (a) is C prepared in example 3 of the present invention 6 N 7 UV-VISIBLE SOLID DIFFUSION SPECTRUM OF CARBON NITRIDE, wherein (b) is C prepared in EXAMPLE 3 of THE INVENTION 6 N 7 Carbon nitride forbidden band width; (c) C prepared for example 3 of the invention 6 N 7 Schottky curve of carbon nitride; (d) C prepared for inventive example 3 6 N 7 A valence band photoelectron spectrum of carbon nitride;
FIG. 13 is a photograph of C prepared in example 3 of the present invention 6 N 7 Electron paramagnetic resonance spectroscopy of carbon nitride;
FIG. 14 shows a graph of C prepared in example 3 of the present invention 6 N 7 Transient surface photovoltage spectra of carbon nitride;
FIG. 15 is C prepared according to example 3 of the present invention 6 N 7 Electrochemical impedance spectroscopy of carbon nitride;
FIG. 16 is C prepared according to example 3 of the present invention 6 N 7 Photocurrent response of carbon nitride;
FIG. 17 is C prepared according to example 3 of the present invention 6 N 7 A line graph of a photocatalytic hydrogen evolution reaction of carbon nitride;
FIG. 18 is C prepared according to example 3 of the present invention 6 N 7 The relationship between the quantum efficiency of carbon nitride and the spectral absorption wavelength;
FIG. 19 is C prepared according to example 3 of the present invention 6 N 7 Detecting a spectrogram of the superoxide radical by using electron paramagnetic resonance in a photocatalytic diphenyl hydrazine oxidation experiment by using carbon nitride;
FIG. 20 shows C prepared in examples 1-5 of the present invention 6 N 7 X-ray powder diffraction of carbon nitride;
FIG. 21 shows C prepared in examples 1-5 of the present invention 6 N 7 A solid diffuse reflectance spectrum of carbon nitride;
FIG. 22 shows C prepared in examples 1-5 of the present invention 6 N 7 Photocatalytic hydrogen production data of carbon nitride;
FIG. 23 is C prepared according to example 6 of the present invention 6 N 7 X-ray powder diffraction pattern of carbon nitride;
FIG. 24 is C prepared according to example 6 of the present invention 6 N 7 A solid diffuse reflectance spectrum of carbon nitride;
FIG. 25 is C prepared according to example 6 of the present invention 6 N 7 Photocatalytic hydrogen production data of carbon nitride;
FIG. 26 is C prepared according to example 7 of the present invention 6 N 7 X-ray powder diffraction of carbon nitride;
FIG. 27 is C prepared according to example 7 of the present invention 6 N 7 A solid diffuse reflectance spectrum of carbon nitride;
FIG. 28 is C prepared according to example 8 of the present invention 6 N 7 X-ray powder diffraction of carbon nitride;
FIG. 29 shows a graph of C prepared in example 8 of the present invention 6 N 7 A solid diffuse reflectance spectrum of carbon nitride;
FIG. 30 is C prepared in examples 7 and 8 of the present invention 6 N 7 Photocatalytic hydrogen production data of carbon nitride;
FIG. 31 shows a drawing C of the present invention 6 N 7 Synthetic scheme for the preparation of carbon nitride.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are disclosed below in conjunction with the detailed description, but it is to be understood that this disclosure is only intended to further illustrate features and advantages of the invention, and is not intended to limit the claims to the invention.
C of the invention 6 N 7 The preparation method of the carbon nitride comprises the following steps:
step one, uniformly mixing a compound A and a compound B according to the mass ratio (1-3) to 1 to obtain a mixture;
step two, reacting the mixture obtained in the step one at the reaction temperature of 425-700 ℃ for more than 1h in air or inert atmosphere, and cooling to obtain C 6 N 7 A carbon nitride material.
In the technical scheme, in the first step, the compound a is one or more of urea, cyanamide and thiourea, and the compound B is one or more of oxalyl diamine and oxalic acid, wherein the mass ratio of the compound a to the compound B is preferably 2. The mode of mixing uniformly is not particularly limited, and it is usually grinding mixing uniformly.
According to the technical scheme, in the second step, the reaction temperature must be controlled to be 425-700 ℃, and if the temperature is lower than 400 ℃, heptazine ring cannot be formed; if the temperature is above 700 ℃, C 6 N 7 Carbon nitride material is unstable leading to thermal decomposition; the reaction temperature is preferably 450 to 650 ℃. The reaction time is preferably 3 hours. The heating apparatus usually employs a muffle furnace. Since the yield is higher when the temperature is raised to the reaction temperature at a temperature raising rate of 20 ℃/min or less, the temperature is preferably raised to the reaction temperature at a temperature raising rate of 20 ℃/min or less, and more preferably at a temperature raising rate of 5 ℃/min.
Taking urea as an example, the invention C 6 N 7 The production route of the carbon nitride material is shown in fig. 31.
C of the invention 6 N 7 The preparation principle of the carbon nitride material is as follows: oxalyldiamide (compound B) can be condensed with urea (compound A) and then deaminated by dehydration to form a heptazine ring, i.e. C, connected by a C-C single bond 6 N 7 Ring to obtain C 6 N 7 A carbon nitride material.
The present invention also provides the above-mentioned compound C 6 N 7 Preparation method of carbon nitride material C 6 N 7 A carbon nitride material.
The present invention also provides the above-mentioned compound C 6 N 7 Use of a carbon nitride material as a photocatalyst. Specifically, the carbon nitride material is used for photocatalytic hydrogen production, photocatalytic carbon dioxide reduction, photocatalytic nitrogen conversion into ammonia gas, photocatalytic diphenylhydrazine oxidation, photocatalytic benzylamine oxidation, photocatalytic phenol degradation, photocatalytic halogenated phenol degradation, photocatalytic tetracycline degradation, photocatalytic methyl orange degradation, photocatalytic Cr degradation 6+ Reduction, photocatalytic removal of NO 2 The use of (1).
Example 1
Step one, grinding and uniformly mixing urea and oxalyl diamine according to a mass ratio of 1;
step two, putting the mixture into a crucible, placing the crucible in a muffle furnace in air atmosphere, reacting for 3 hours at 600 ℃, taking out the crucible, and cooling to obtain C 6 N 7 A carbon nitride material.
Example 2
Step one, grinding and uniformly mixing urea and oxalyl diamine according to the mass ratio of 1.5 to obtain a mixture;
step two, placing the mixture into a crucible, placing the crucible in a muffle furnace under air atmosphere, reacting for 3 hours at 600 ℃, taking out the crucible, and cooling to obtain C 6 N 7 A carbon nitride material.
Example 3
Step one, grinding and uniformly mixing urea and oxalyl diamine according to the mass ratio of 2;
step two, putting the mixture into a crucible, placing the crucible in a muffle furnace in air atmosphere, reacting for 3 hours at 600 ℃, taking out the crucible, and cooling to obtain C 6 N 7 A carbon nitride material.
Example 4
Step one, grinding and uniformly mixing urea and oxalyl diamine according to the mass ratio of 2.5;
step two, putting the mixture into a crucible, placing the crucible in a muffle furnace in air atmosphere, reacting for 3 hours at 600 ℃, taking out the crucible, and cooling to obtain C 6 N 7 A carbon nitride material.
Example 5
Step one, grinding and uniformly mixing urea and oxalyl diamine according to the mass ratio of 3;
step two, putting the mixture into a crucible, placing the crucible in a muffle furnace in air atmosphere, reacting for 3 hours at 600 ℃, taking out the crucible, and cooling to obtain C 6 N 7 A carbon nitride material.
Example 6
Step one, grinding and uniformly mixing urea and oxalyl diamine according to the mass ratio of 2;
step two, mixingPlacing the mixture in a crucible, placing in a muffle furnace under air atmosphere, reacting at 500 deg.C, 550 deg.C, 600 deg.C and 650 deg.C for 3 hr, taking out the crucible, and cooling to obtain C 6 N 7 A carbon nitride material.
Example 7
Step one, grinding and uniformly mixing cyanamide and oxalyl diamine according to the mass ratio of 2;
step two, putting the mixture into a crucible, putting the crucible into a muffle furnace in the air atmosphere, reacting for 3 hours at 500 ℃, 550 ℃, 600 ℃ and 650 ℃ respectively, taking out the crucible, and cooling to obtain the compound C 6 N 7 A carbon nitride material.
Example 8
Step one, grinding and uniformly mixing thiourea and oxalyl diamine according to the mass ratio of 2;
step two, putting the mixture into a crucible, putting the crucible into a muffle furnace in the air atmosphere, reacting for 3 hours at 500 ℃, 550 ℃, 600 ℃ and 650 ℃ respectively, taking out the crucible, and cooling to obtain the compound C 6 N 7 A carbon nitride material.
The physical and chemical properties of the carbon nitride materials obtained in examples 1 to 8 were examined.
In FIG. 1, (a) is C of example 3 6 N 7 The scanning electron microscope of (2) is shown in the drawing (10 μm), and C is shown in the drawing 6 N 7 Has a porous layered structure and rough and uneven surface. (b) Is C of example 3 6 N 7 Picture (2 μm) of a scanning electron microscope of (1), as can be seen from the figure, C 6 N 7 The sheets of (a) are very small and are interconnected to form a porous structure, similar to a sponge. (c) Is C 6 N 7 Transmission electron microscope picture (100 nm), from which it can also be seen that C 6 N 7 The porous structure has pore diameters of tens or hundreds of nanometers, and the layers are stacked and the pore diameters are covered. (d) Is C 6 N 7 No significant lattice fringes were found from the transmission electron microscope picture (10 nm), which also demonstrates C 6 N 7 Disordered structure of。
FIG. 2 is C prepared in example 3 6 N 7 The atomic force microscope picture of (a) shows that the nanosheets are relatively uniform.
FIG. 3 shows the thickness of the nanosheet partially scanned by the solid line of FIG. 2, from which it can be seen that the nanosheet has a thickness of 0.81nm, corresponding to 2-3 layers C 6 N 7 Of (c) is used.
FIG. 4 is C prepared in example 3 6 N 7 As can be seen from FIG. 4 and Table 1, the element contents were 45.02% (C), 53.41% (N) and 1.57% (O), respectively, and the C/N ratio was 0.843, corresponding to C 6 N 7 C/N of (1).
TABLE 1C of example 3 6 N 7 Energy spectrum analysis of X-ray
| Element(s) | Atom (%) | Mass (%) |
| C | 41.15 | 45.02 |
| N | 56.94 | 53.41 |
| O | 1.91 | 1.57 |
Table 2 shows C prepared in example 3 6 N 7 Elemental analysis of (2); the C/N ratio of 0.83, which is close to the result of X-ray spectral analysis, is found from the table, demonstrating that the carbon nitride material having the structure C prepared by the above method 6 N 7 。
Table 2 example 3C 6 N 7 Elemental analysis of
| Sample (I) | C/wt％ | N/wt％ | C/N |
| C 6 N 7 | 37.648 | 53.003 | 0.83 |
FIG. 5 is C prepared in example 3 6 N 7 X-ray powder diffraction pattern of (a). M-C 6 N 7 C prepared for example 3 6 N 7 And treating the obtained product by a molten salt method. The specific method comprises the following steps: 0.6g of C prepared in example 3 was charged 6 N 7 3.3g of KCl and 2.7g of LiCl were ground in a glove box and the powder was calcined at a temperature of 500 ℃ for 4 hours at a rate of 5 ℃/min under an argon atmosphere. Normalized C 6 N 7 Simulated for theoretical calculation C 6 N 7 XRD of (a). As can be seen from the figure, C prepared by the present invention 6 N 7 The amorphous structure has very low crystallinity and shows a broad peak in a wide range. At M-C 6 N 7 In, the peak at 8.23 corresponds to (100)The crystal plane is a peak due to an in-plane repeating unit. The peak at 26.3 corresponds to the (002) plane, a peak due to stacking between layers, which is the same as the peak position simulated by theoretical calculation. In addition, C of the theoretical calculation simulation 6 N 7 The peaks at the middle 14.47 °, 21.5 °, 26.8 °, 28.2 °, 30.54 °, 43.5 ° and 44.5 ° all agree with the experimental values, which proves that the C prepared by the invention 6 N 7 Consistent with the intended structure.
FIG. 6 is C prepared in example 3 6 N 7 Of (2) a solid 13 C nuclear magnetic map, the peak at a chemical shift value of 164.4ppm is attributed to C- (C-N = C) and a small fraction of C-N 2 NH and CN 2 NH 2 The peak at a chemical shift of 156ppm is attributed to C-N 3 。
FIG. 7 is C prepared in example 3 6 N 7 The peaks at 142.6ppm, 145.1ppm, 145.7ppm, 145.9ppm, 153.6ppm and 157.3ppm are attributed to sp and sp < SP > respectively 3 Signals of corner carbons (δ =154-160 ppm) and bay carbons (δ =143-147 ppm) of N-linked heptazine units. The signals at 156.3ppm, 146.1ppm and 141.4ppm may be attributed to the horn and gulf carbons of the heptazine unit, respectively, caused by the C-C bond. The signals at 149.9ppm, 151.1ppm, 151.7ppm, 152.2ppm and 152.5ppm belong to the incompletely polymerized amide and urea fragments.
FIG. 8 is C prepared in example 3 6 N 7 X-ray photoelectron spectroscopy. Wherein (a) is XPS fine spectrogram of C, can be divided into four peaks when the binding energy is 284.5ev, 286.3ev, 287.6ev and 288.2ev respectively, and are respectively assigned to impurity carbon (graphite C = C or grease) and C-NH in heptazine ring x Incompletely polymerized (C (O) NH x ) And sp 2 Hybrid carbon (N-C = N). The peak at 285.4ev can be attributed to the C-C bond in oxalyldiamine, further confirming the successful introduction of the C-C bond. (b) The peaks at 398.1eV, 398.8eV, 400.1eV and 400.9eV correspond to the (C (O) NH in the heptazine ring, respectively, for the XPS fine spectrum for N1s x )、C-N＝C、 N(C) 3 and-NH x 。
FIG. 9 is C prepared in example 3 6 N 7 An infrared spectrum of (1). As can be seen in the figure, 1700-700cm -1 The peak in the range of (1) is due to a derivative of heptazine ring. 3427cm -1 、1206cm -1 And 1456cm -1 Disappearance of the peak represents-NH x And (4) reduction of components.
FIG. 10 is C prepared in example 3 6 N 7 The raman spectrum of (a). As can be seen from the figure, C 6 N 7 Is composed of heptazine ring and its derivative.
FIG. 11 is C prepared in example 3 6 N 7 N of (A) 2 Adsorption graph, C 6 N 7 Has a specific surface area of 87.14 m 2 ·g -1 The surface of the sample is rough and porous, but the specific surface area of the product is not very high due to mutual masking between layers.
In FIG. 12, (a) is C prepared in example 3 6 N 7 Solid diffuse reflection of (1), as can be seen from the figure, C 6 N 7 The absorption in ultraviolet region, visible region and even near infrared region is very good. (b) Is a curve of forbidden band width calculated by a Tauc method from solid diffuse reflection data, and can be seen from the graph, C prepared in example 3 6 N 7 The forbidden band width of (A) is 2.05eV, and the absorption sideband is calculated to be 604nm. (c) C prepared for example 3 6 N 7 Schottky curve (measured electrochemically) of (D), to yield C 6 N 7 CB of (b) is-0.04V, indicating C 6 N 7 Has the thermodynamic condition of hydrogen energy produced by photocatalytic water decomposition. (d) C prepared for example 3 6 N 7 Valence band photoelectron spectrum, C 6 N 7 The valence band of (A) is 2.01V, indicating C 6 N 7 Has very good oxidizability.
FIG. 13 is C prepared in example 3 6 N 7 Electron paramagnetic resonance spectrum of (1), as can be seen from the figure, C 6 N 7 The presence of unpaired single electron in C also proves that 6 N 7 Has high conjugation property and forms electron delocalization in a large range.
FIG. 14 is C prepared in example 3 6 N 7 Transient surface photovoltage spectrum of (1), as can be seen from the figure, photoexcitationA large number of photogenerated electrons are generated, and an electron bleaching process exists, which promotes the separation of carriers, so that more electrons have the opportunity to migrate to the surface of the material to perform catalytic reaction.
FIG. 15 is C prepared in example 3 6 N 7 Electrochemical impedance spectroscopy, as can be seen from the figure, C 6 N 7 Has certain conductivity.
FIG. 16 is C prepared in example 3 6 N 7 The photocurrent response of (C) can be seen from the figure 6 N 7 Has response to visible light, generates a large amount of photo-generated electrons, and has good conductivity, which is consistent with the conclusion obtained by electrochemical impedance spectroscopy.
FIG. 17 is C prepared in example 3 6 N 7 The curve diagram of the photocatalytic hydrogen evolution reaction of (1) is shown, the reaction is carried out under vacuum condition, the total volume of the reaction is 121.2ml, wherein, the dosage of the catalyst is 10mg, the volume of the water is 90ml, the volume of the sacrificial agent triethanolamine is 30ml, and the volume of the cocatalyst chloroplatinic acid (1%) is 1.2ml. Obtained through experiments, C 6 N 7 The hydrogen yield per hour of the photocatalysis is 79.46 mu mol, and the photocatalysis hydrogen production has good stability and still maintains the original catalytic activity after 15h of circulation. C is to be 6 N 7 After ultrasonic peeling (peeling method: 0.1 gC) 6 N 7 Placing in 400ml distilled water, ultrasonically stripping for 9h at 1500 rpm, centrifuging the obtained product for 10min at 8000 rpm) to obtain higher hydrogen production efficiency of 10.86 mmol.h -1 ·g -1 。
FIG. 18 is C prepared in example 3 6 N 7 The relationship between the quantum efficiency and the spectral absorption wavelength of (a); as can be seen from the graph, the quantum efficiency at a wavelength of 420nm was 36.12%, and the quantum efficiencies at wavelengths of 500nm, 550nm and 600nm were 2.41%, 0.96% and 0.33%, indicating that C is present 6 N 7 Has good photocatalytic hydrogen production activity with visible light response.
For C prepared in example 3 6 N 7 Experiments were performed with photocatalytic diphenylhydrazine oxidation. The experimental conditions were: mixing 5mlAcetonitrile, 0.1mmol of diphenylhydrazine and 10mg of catalyst are added into a quartz tube, the quartz tube is placed under an LED with the wavelength of 420-425nm for reaction for 2-4.5h or for reaction for 4.5h in a dark place, the product after the reaction is centrifugally separated, and 2 mu l of the product is taken and enters a gas chromatograph for qualitative and quantitative determination of a sample. Specific reaction conditions and detection results are shown in table 3.
The reaction equation is:
TABLE 3
As can be seen from Table 3, in the absence of C 6 N 7 In the process, the diphenylhydrazine has certain oxidizability under the irradiation of LED light, and the conversion rate after 4.5 hours is 13.9%. But if C is present 6 N 7 In the absence of light, the reaction did not substantially occur, which fully illustrates the importance of light for the oxidation of hydrazobenzene. When the reaction is carried out according to the experimental conditions of the number 3, the conversion rate of the reaction is greatly improved, and the diphenylhydrazine is basically completely converted within 4.5 hours. And the original reactivity is still maintained after five to ten cycles of circulation. For C 6 N 7 In the experiment of photocatalytic oxidation of diphenylhydrazine, oxygen also has a decisive role in the reaction effect. The addition of an electron trapping agent or a hole trapping agent does not influence the experimental result, which shows that in the photocatalytic system, electrons and holes are not main active species influencing the oxidation of the photocatalytic hydrazobenzene.
FIG. 19 is C prepared in example 3 6 N 7 Detecting a spectrogram of the superoxide radical by using electron paramagnetic resonance in a photocatalytic diphenyl hydrazine oxidation experiment; it is shown that the superoxide radical does promote the oxidation of hydrazobenzene.
For C prepared in example 3 6 N 7 The results of the photocatalytic degradation of phenol and halophenol are shown in Table 4.
TABLE 4 (C) of example 3 6 N 7 ) n Experimental results of photocatalytic degradation of phenol and halophenol
As can be seen in Table 4, 20mg of C 6 N 7 Can degrade phenol of 10ppm by 68.8 percent within 180min, has excellent degradation activity to halogenated phenol, and has the following effects: p-chlorophenol (120min, 51%), 2, 4-difluorophenol (60min, 42%), 2, 4-dichlorophenol (120min, 100%), 2, 4-dibromophenol (80min, 100%).
FIG. 20 shows C in examples 1 to 5 6 N 7 X-ray powder diffraction of (2), as can be seen from the figure, C of examples 1 to 5 6 N 7 The X-ray powder diffraction of (a) was about the same, indicating that the framework of the resulting structure was essentially unchanged. As the oxalyldiamide content increases, the structure of the product tends to be more disordered.
FIG. 21 shows C in examples 1 to 5 6 N 7 As can be seen from the solid diffuse reflectance spectrum of (A), C of examples 1 to 5 6 N 7 The absorption spectra of (a) are approximately the same.
FIG. 22 shows C in examples 1 to 5 6 N 7 The data of the photocatalytic hydrogen production shows that the yield of the photocatalytic hydrogen evolution is respectively 0.1 mu mol/h, 8.9 mu mol/h, 70.76 mu mol/h, 25.3 mu mol/h and 4.2 mu mol/h. Wherein n is Urea ：n Oxalyl diamines The yield was the highest and was the optimum value when = 2.
FIG. 23 shows a drawing C of example 6 6 N 7 X-ray powder diffraction pattern of (a); as can be seen from FIG. 23, at different heating temperatures, C 6 N 7 The peaks having (001) and (002) crystal planes still remained, and the crystallinity was slightly increased with the increase of temperature.
FIG. 24 shows a drawing C of example 6 6 N 7 As can be seen from FIG. 24, the solid diffuse reflectance spectrum of (C) obtained at different temperatures 6 N 7 Absorption spectrum ofAre substantially identical.
FIG. 25 shows a drawing C in example 6 6 N 7 The photocatalytic hydrogen production data of (1) can be seen from FIG. 25, C prepared at 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C 6 N 7 The photocatalytic hydrogen production amounts of (A) were 10.2. Mu. Mol/h, 18.6. Mu. Mol/h, 79.9. Mu. Mol/h, and 24.3. Mu. Mol/h, respectively, and the experimental conditions were as shown in FIG. 17.
FIG. 26 shows a drawing C of example 7 6 N 7 As can be seen from fig. 26, the crystallinity of the product increases with increasing temperature.
FIG. 27 shows C of example 7 6 N 7 (ii) solid diffuse reflectance spectrum of (D), as can be seen from FIG. 27, C 6 N 7 The absorption side bands are expanded to about 600 nm.
FIG. 28 shows C of example 8 6 N 7 X-ray powder diffraction of (2), C prepared at different temperatures, as can be seen from FIG. 28 6 N 7 There was no significant difference in XRD curves.
FIG. 29 shows C in example 8 6 N 7 Solid diffuse reflectance spectrum of (A), as can be seen from FIG. 29, C prepared at different temperatures 6 N 7 The uv absorption ranges of (a) are about the same, indicating that the structure is essentially unchanged.
FIG. 30 shows C at 600 ℃ prepared in examples 7 and 8 6 N 7 The experimental conditions of the photocatalytic hydrogen production were the same as those used in fig. 17, and the hydrogen production amounts were 0.68 μmol/h and 0.7 μmol/h, respectively.
All of the above are illustrative of C of the present invention 6 N 7 Has porous layered structure, good conductivity, good visible light response and high photocatalytic activity.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (9)
1.C 6 N 7 The preparation method of the carbon nitride material is characterized by comprising the following steps of:
step one, uniformly mixing a compound A and a compound B according to the mass ratio (1-3) to 1 to obtain a mixture;
the compound A is one or more of urea, cyanamide and thiourea;
the compound B is one or more of oxalyl diamine and oxalic acid;
step two, under the air or inert atmosphere, the mixture obtained in the step one reacts for more than 1h at the reaction temperature of 425-700 ℃, and is cooled to obtain C 6 N 7 A carbon nitride material.
2. C according to claim 1 6 N 7 A method for producing a carbon nitride material, characterized in that the mass ratio of the compound A to the compound B is 2.
3. The C of claim 1 6 N 7 The preparation method of the carbon nitride material is characterized in that the reaction temperature is 450-650 ℃.
4. C according to claim 1 6 N 7 The preparation method of the carbon nitride material is characterized in that the reaction time is 3h.
5. The C of claim 1 6 N 7 A method for producing a carbon nitride material, characterized in that the temperature is raised to the reaction temperature at a temperature raising rate of 20 ℃/min or less.
6. C according to claim 5 6 N 7 The preparation method of the carbon nitride material is characterized in that the heating rate is 5 ℃/min.
7. C according to any of claims 1 to 6 6 N 7 Preparation method of carbon nitride material C 6 N 7 A carbon nitride material.
8. C of claim 7 6 N 7 Use of a carbon nitride material as a photocatalyst.
9. C according to claim 8 6 N 7 Use of a carbon nitride material as a photocatalyst, characterized in that C 6 N 7 Carbon nitride material in photocatalysis hydrogen production, photocatalysis carbon dioxide reduction, photocatalysis nitrogen gas conversion into ammonia gas, photocatalysis diphenyl hydrazine oxidation, photocatalysis benzylamine oxidation, photocatalysis phenol degradation, photocatalysis halogenated phenol degradation, photocatalysis tetracycline degradation, photocatalysis methyl orange degradation, photocatalysis Cr 6+ Reduction, photocatalytic removal of NO 2 The use of (1).
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