CN113210005A - Cl-doped C3N5And method for preparing the same - Google Patents

Cl-doped C3N5And method for preparing the same Download PDF

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CN113210005A
CN113210005A CN202110614760.1A CN202110614760A CN113210005A CN 113210005 A CN113210005 A CN 113210005A CN 202110614760 A CN202110614760 A CN 202110614760A CN 113210005 A CN113210005 A CN 113210005A
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membered nitrogen
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CN113210005B (en
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杜海英
余泳
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Chengdu Univeristy of Technology
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Abstract

The invention relates to Cl-doped C3N5And a preparation method thereof, belonging to the technical field of photocatalysis. Cl-doped C of the invention3N5The content of Cl in the solution is 0.05-15 wt%. Cl-doped C of the invention3N5The preparation method comprises the following steps: fully and uniformly mixing ammonium chloride, 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid; heating the uniformly mixed powder, preserving the heat for more than 1.5h at 500-550 ℃, cooling, taking out, washing and drying to obtain ClDoped C3N5The calcination is carried out in an air or nitrogen atmosphere. Successful doping of Cl to C of the invention3N5And the band gap value is low, which is beneficial to photocatalysis. Cl-doped C of the invention3N5Porosity ratio C3N5And also increases.

Description

Cl-doped C3N5And method for preparing the same
Technical Field
The invention relates to Cl-doped C3N5And a preparation method thereof, belonging to the technical field of photocatalysis.
Background
Hydrogen is of great interest as a sustainable clean fuel due to its high energy density. The carbon-nitrogen compound photocatalyst is an important catalyst for producing hydrogen. The carbonitride compound photocatalyst has C3N4、C3N5And the like. Carbon nitride C3N4Due to their low density, high thermal stability is of great interest. High chemical stability and biocompatibility. These properties make it possible to apply to gas storage, photocatalysis and sensing. Despite these advantages, C is due to the rapid recombination of photogenerated carriers and low surface area3N4Is limited in its utility.
C3N5The compound structure has a high nitrogen content and shows extraordinary performance in photocatalysis and gas phase reactions. Compared with the prior C which is more researched3N4Comparison of materials, C3N5Has higher diffusion limit current density and lower overpotential, so that the photocatalysis performance is better. But the photocatalytic performance is yet to be further improved.
C currently doped with Cl3N4Materials, for example, Cao M, Wang K, Tudela I, et al, improved photocatalytic performance of g-C3N4 through balancing the interstitial and substitutional chlorine doping[J]Applied Surface Science,2021,536:147784 discloses the addition of cyanuric chloride, dicyandiamide and acetonitrile to a teflon lined autoclave. During the synthesis, the reactor was kept at 10 ℃ for min-1The heating rate of (3) is increased to 180 ℃. The mixture was kept under stirring during immersion at 180 ℃ for 48 hours. Naturally cooling to room temperature, washing and drying to obtain Cl-doped C3N4A material.
Futao,Yi,Huihui,et al.Sulfur-and chlorine-co-doped g-C3N4 nanosheets with enhanced active species generation for boosting visible-light photodegradation activity-ScienceDirect[J].Separation&Purification Technology,233:115997-3N4The preparation method of (1) was carried out by mixing 10.0g of thiourea with different amounts of ammonium chloride in an agate mortar and grinding for 30 minutes. After milling, the precursor was heated at 550 ℃ for 2h with a heating rate of 2 ℃/min. The yellow product was washed several times with absolute ethanol and deionized water. Finally, the precipitate obtained is dried at 80 ℃ for 12 h. To obtain S/Cl codoped C3N4。
However, there is currently no Cl-doped C3N5Production of Cl-doped C3N4For Cl-doped C3N5The synthesis of (A) also has no reference meaning. Because C is currently produced3N5One of the main raw materials is 3-amino-1, 2, 4-triazole. 3-amino-1, 2, 4-triazole readily reacts with NH4The Cl reacts. For example, Liu T, Yang G, Wang W, et al preparation of C3N5 nanosheets with enhanced performance in photocatalytic methyl ethylene (MB) deletion and H2-evolution from water splitting[J]Environmental Research,2020,188 (11: 109741 discloses the use of 3-amino-1, 2, 4-triazole (3-AT) and NH4Cl is thermally treated at 550 ℃ for 3h to react to generate C3N5Although a large amount of NH is employed4Cl, but NH4Cl readily reacts with 3-amino-1, 2, 4-triazole to form C3N5The reaction principle is shown in detail in FIG. 13. The Cl of the catalyst does not participate in bonding and is not doped into C3N5In (1). How to synthesize Cl-doped C3N5Improving C3N5Performance of, further improving C3N5The photocatalytic performance of (a), which is a problem to be solved by those skilled in the art.
Disclosure of Invention
The first problem to be solved by the present invention is to provide a Cl-doped C3N5。
To solve the first technical problem of the present invention, the Cl-doped C3N5The content of Cl in the solution is 0.05-15 wt%; preferably 0.1 to 1.0 wt%.
In a toolIn one embodiment, the Cl-doped C3N5The preparation method comprises the following steps:
a. mixing materials: fully and uniformly mixing ammonium chloride, 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
b. and (3) calcining: heating the uniformly mixed powder, preserving heat for more than 1.5 hours at 500-550 ℃, preferably preserving heat for 2-4 hours, cooling, taking out, washing and drying to obtain Cl-doped C3N5The calcination is carried out in an air or nitrogen atmosphere, preferably a nitrogen atmosphere.
In a specific embodiment, the mass ratio of the ammonium chloride to the 3-amino-1, 2, 4-triazole to the six-membered nitrogen heterocycle is 0.02-0.30: 1: 1.1-1.45; preferably, the hexatomic nitrogen heterocycle is cyanuric acid and barbituric acid, and the mass ratio of the cyanuric acid to the barbituric acid is 1: 0.1-0.45.
In a specific embodiment, the method further comprises the step of adding the fully and uniformly mixed powder obtained in the step a into an auxiliary agent solution, stirring, drying, and then carrying out the step b on the dried powder; the auxiliary agent is potassium salt; the potassium salt is preferably at least one of potassium bromide, potassium chloride or potassium iodide, and the mass ratio of the auxiliary agent to the uniformly mixed powder is preferably 0-4%.
In one embodiment, the Cl-doped C3N5The band gap value of (A) is 1.16-1.22 eV, preferably 1.16 eV.
In one embodiment, the Cl-doped C3N5Has a specific surface area of 3.24m2/g～11.23m2/g。
The second technical problem to be solved by the invention is to provide C doped with Cl3N5The preparation method of (1).
To solve the second technical problem of the present invention, the method includes:
a. mixing materials: fully and uniformly mixing ammonium chloride, 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
b. and (3) calcining: heating the uniformly mixed powder, preserving heat for more than 1.5 hours at 500-550 ℃, preferably preserving heat for 2-4 hours, cooling, taking out, washing and drying to obtain Cl-doped C3N5The calcination is carried out in an air or nitrogen atmosphere, preferably a nitrogen atmosphere.
In a specific embodiment, the mass ratio of the ammonium chloride to the 3-amino-1, 2, 4-triazole to the six-membered nitrogen heterocycle is 0.02-0.30: 1: 1.1-1.45; preferably, the hexatomic nitrogen heterocycle is cyanuric acid and barbituric acid, and the mass ratio of the cyanuric acid to the barbituric acid is 1: 0.1-0.45.
In a specific embodiment, the method further comprises the step of adding the fully and uniformly mixed powder obtained in the step a into an auxiliary agent solution, stirring, drying, and then carrying out the step b on the dried powder; the auxiliary agent is potassium salt; the potassium salt is at least one of potassium bromide, potassium chloride or potassium iodide, and the mass ratio of the auxiliary agent to the uniformly mixed powder is preferably 0-4%.
In one embodiment, the stirring is at ambient temperature for more than 1 hour followed by sonication at room temperature for more than 1 hour.
Has the advantages that:
(1) successful doping of Cl to C of the invention3N5Middle, band gap value compared with C3N5Further reducing the cost and being beneficial to photocatalysis.
(2) Cl-doped C of the invention3N5Specific surface area ratio C3N5And also increases.
Drawings
FIG. 1 is XRD patterns of examples 1-6 and comparative example 1;
FIG. 2 is a graph showing UV-VIS absorption of examples 2-6 and comparative example 1;
FIG. 3 is a graph showing the diffuse reflectance of ultraviolet light of examples 2 to 6 and comparative example 1;
FIG. 4 is a UV diffuse reflectance spectrum of example 5;
FIG. 5 is a UV diffuse reflectance spectrum of comparative example 1;
FIG. 6 shows examples 2 and 5 and comparative example1C with 420nm low-pass cut-off filter added under 366nm excitation3N5(ii) a fluorescence emission spectrum of;
FIG. 7 is a graph showing infrared absorption spectra of examples 1 to 6 and comparative example 1;
FIG. 8 is an energy spectrum of example 3;
FIG. 9 is an SEM photograph of the product of example 2 at 5000 magnification;
FIG. 10 is an SEM photograph of the product of example 3 at 5000 magnification;
FIG. 11 is a SEM photograph of the product of example 5 at 5000 magnification;
FIG. 12 is an SEM photograph of the product of comparative example 1 at 5000 magnification;
FIG. 13 shows conventional 3-amino-1, 2, 4-triazole (3-AT) and NH4Principle of Cl reaction.
Detailed Description
In order to solve the first technical problem of the invention, the Cl content of the Cl-doped C3N5 is 0.05-15 wt%; preferably 0.1 to 1.0 wt%.
In one embodiment, the Cl-doped C3N5The preparation method comprises the following steps:
a. mixing materials: fully and uniformly mixing ammonium chloride, 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
b. and (3) calcining: heating the uniformly mixed powder, preserving heat for more than 1.5 hours at 500-550 ℃, preferably preserving heat for 2-4 hours, cooling, taking out, washing and drying to obtain Cl-doped C3N5The calcination is carried out in an air or nitrogen atmosphere, preferably a nitrogen atmosphere.
In a specific embodiment, the mass ratio of the ammonium chloride to the 3-amino-1, 2, 4-triazole to the six-membered nitrogen heterocycle is 0.02-0.30: 1: 1.1-1.45; preferably, the hexatomic nitrogen heterocycle is cyanuric acid and barbituric acid, and the mass ratio of the cyanuric acid to the barbituric acid is 1: 0.1-0.45.
In a specific embodiment, the method further comprises the step of adding the fully and uniformly mixed powder obtained in the step a into an auxiliary agent solution, stirring, drying, and then carrying out the step b on the dried powder; the auxiliary agent is potassium salt; the potassium salt is preferably at least one of potassium bromide, potassium chloride or potassium iodide, and the mass ratio of the auxiliary agent to the uniformly mixed powder is preferably 0-4%.
In one embodiment, the Cl-doped C3N5The band gap value of (A) is 1.16-1.22 eV, preferably 1.16 eV.
In one embodiment, the Cl-doped C3N5Has a specific surface area of 3.24m2/g～11.23m2/g。
To solve the second technical problem of the present invention, the method includes:
a. mixing materials: fully and uniformly mixing ammonium chloride, 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
b. and (3) calcining: heating the uniformly mixed powder, preserving heat for more than 1.5 hours at 500-550 ℃, preferably preserving heat for 2-4 hours, cooling, taking out, washing and drying to obtain Cl-doped C3N5The calcination is carried out in an air or nitrogen atmosphere, preferably a nitrogen atmosphere.
In a specific embodiment, the mass ratio of the ammonium chloride to the 3-amino-1, 2, 4-triazole to the six-membered nitrogen heterocycle is 0.02-0.30: 1: 1.1-1.45; preferably, the hexatomic nitrogen heterocycle is cyanuric acid and barbituric acid, and the mass ratio of the cyanuric acid to the barbituric acid is 1: 0.1-0.45.
In a specific embodiment, the method further comprises the step of adding the fully and uniformly mixed powder obtained in the step a into an auxiliary agent solution, stirring, drying, and then carrying out the step b on the dried powder; the auxiliary agent is potassium salt; the potassium salt is at least one of potassium bromide, potassium chloride or potassium iodide, and the mass ratio of the auxiliary agent to the uniformly mixed powder is preferably 0-4%.
In one embodiment, the stirring is at ambient temperature for more than 1 hour followed by sonication at room temperature for more than 1 hour.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
1.0g of 3-amino-1, 2, 4-triazole, 1.0g of cyanuric acid, 0.02g of ammonium chloride, 0.07g of KBr and 0.45g of barbituric acid are each weighed into a beaker and 25mL of deionized water are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. The suspension was then dried in an oven at 70 ℃ to give a powder. The crucible is moved into a 10mL crucible with a cover, and is moved into a tube furnace to be heated to 500 ℃ at the heating rate of 5 ℃/min, and then the temperature is kept for 3 h. After natural cooling, the sample is put into a beaker, 100mL of distilled water is added, then the beaker is put into an ultrasonic machine for ultrasonic dispersion for 3 hours, and the sample is washed for a plurality of times, centrifuged and dried. The label is 1Cl-C3N5And (3) sampling. The Cl content in the product was 0.06 wt%. The specific surface area is 3.58m2(ii) in terms of/g. The band gap value was 1.22 eV.
Example 2
1.0g of 3-amino-1, 2, 4-triazole, 1.0g of cyanuric acid, 0.04g of ammonium chloride, 0.07g of KBr and 0.45g of barbituric acid are each weighed into a beaker and 25mL of deionized water are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. The suspension was then dried in an oven at 70 ℃ to give a powder. The crucible is moved into a 10mL crucible with a cover, and is moved into a tube furnace to be heated to 500 ℃ at the heating rate of 5 ℃/min, and then the temperature is kept for 3 h. After natural cooling, the sample is put into a beaker, 100mL of distilled water is added, then the beaker is put into an ultrasonic machine for ultrasonic dispersion for 3 hours, and the sample is washed for a plurality of times, centrifuged and dried. The label is 2Cl-C3N5And (3) sampling. The Cl content in the product was 0.12 wt%. The specific surface area is 5.69m2(ii) in terms of/g. The band gap value was 1.21 eV.
Example 3
1.0g of 3-amino-1, 2, 4-triazole, 1.0g of cyanuric acid, 0.06g of ammonium chloride, 0.07g of KBr and 0.45g of barbituric acid are each weighed into a beaker and 25mL of deionized water are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. Then putting the suspension into an oven at 70 ℃ for drying to obtain powder. The crucible is moved into a 10mL crucible with a cover, and is moved into a tube furnace to be heated to 500 ℃ at the heating rate of 5 ℃/min, and then the temperature is kept for 3 h. After natural cooling, the sample is put into a beaker, 100mL of distilled water is added, then the beaker is put into an ultrasonic machine for ultrasonic dispersion for 3 hours, and the sample is washed for a plurality of times, centrifuged and dried. The label is 3Cl-C3N5And (3) sampling. The Cl content in the product was 0.18 wt%, and the specific surface area was 6.402m2(ii) in terms of/g. The band gap value was 1.20 eV.
TABLE 13 Cl-C of example 33N5Intelligent quantitative results of energy spectrum
Figure BDA0003096923990000051
Example 4
1.0g of 3-amino-1, 2, 4-triazole, 1.0g of cyanuric acid, 0.10g of ammonium chloride, 0.07g of KBr and 0.45g of barbituric acid are each weighed into a beaker and 25mL of deionized water are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. The suspension was then dried in an oven at 70 ℃ to give a powder. The crucible is moved into a 10mL crucible with a cover, and is moved into a tube furnace to be heated to 500 ℃ at the heating rate of 5 ℃/min, and then the temperature is kept for 3 h. After natural cooling, the sample is put into a beaker, 100mL of distilled water is added, then the beaker is put into an ultrasonic machine for ultrasonic dispersion for 3 hours, and the sample is washed for a plurality of times, centrifuged and dried. The label is 5Cl-C3N5And (3) sampling. The Cl content in the product was 0.30 wt%. Specific surface area of 7.002m2Per gram of wool. The band gap value was 1.19 eV.
Example 5
1.0g of 3-amino-1, 2, 4-triazole, 1.0g of cyanuric acid, 0.20g of ammonium chloride, 0.07g of KBr and 0.45g of barbituric acid are each weighed into a beaker and 25mL of deionized water are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. The suspension was then dried in an oven at 70 ℃ to give a powder. The crucible is moved into a 10mL crucible with a cover, and is moved into a tube furnace to be heated to 500 ℃ at the heating rate of 5 ℃/min, and then the temperature is kept for 3 h. After natural cooling, the sample was filled into a beaker and 100mL of distilled water was added, thenThen putting the sample into an ultrasonic machine for ultrasonic dispersion for 3 hours, washing the sample for a plurality of times, centrifuging and drying the sample. The label is 10Cl-C3N5And (3) sampling. The Cl content in the product was 0.60 wt%. The specific surface area is 10.29m2(ii) in terms of/g. From fig. 3 and 4, it can be seen that the band gap value is 1.16 eV.
Example 6
1.0g of 3-amino-1, 2, 4-triazole, 1.0g of cyanuric acid, 0.30g of ammonium chloride, 0.07g of KBr and 0.45g of barbituric acid are each weighed into a beaker and 25mL of deionized water are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. The suspension was then dried in an oven at 70 ℃ to give a powder. The crucible is moved into a 10mL crucible with a cover, and is moved into a tube furnace to be heated to 500 ℃ at the heating rate of 5 ℃/min, and then the temperature is kept for 3 h. After natural cooling, the sample is put into a beaker, 100mL of distilled water is added, then the beaker is put into an ultrasonic machine for ultrasonic dispersion for 3 hours, and the sample is washed for a plurality of times, centrifuged and dried. The label is 15Cl-C3N5And (3) sampling. The Cl content in the product was 0.90 wt%. Specific surface area of 9.873m2Per gram of wool. The band gap value was 1.19 eV.
Comparative example 1
4.5g of 3-amino-1, 2, 4-triazole, 4.5g of cyanuric acid, 0.3g of KBr and 0.45g of barbituric acid are each weighed into a beaker and 100mL of deionized water are added, and the suspension is stirred at ambient temperature for 2h and then sonicated at room temperature for 1 h. The suspension was then dried in an oven at 70 ℃ to give a powder. The mixture was transferred into a 50mL crucible with a lid, transferred to a tube furnace to be heated to 500 ℃ at a heating rate of 5 ℃/min and then kept for 3 hours. After natural cooling, the sample is put into a beaker, 100mL of distilled water is added, then the beaker is put into an ultrasonic machine for ultrasonic dispersion for 3 hours, and the sample is washed for a plurality of times, centrifuged and dried. The label is C3N5And (3) sampling. It can be seen from fig. 3 and 5 that the band gap value is 1.23 eV. Specific surface area 1.64m2/g。

Claims (10)

  1. Cl-doped C3N5Characterized in that said Cl-doped C3N5The content of Cl in the solution is 0.05-15 wt%; preferably 0.1 to 1.0 wt%.
  2. 2. The Cl-doped C of claim 13N5Characterized in that said Cl-doped C3N5The preparation method comprises the following steps:
    a. mixing materials: fully and uniformly mixing ammonium chloride, 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
    b. and (3) calcining: heating the uniformly mixed powder, preserving heat for more than 1.5 hours at 500-550 ℃, preferably preserving heat for 2-4 hours, cooling, taking out, washing and drying to obtain Cl-doped C3N5The calcination is carried out in an air or nitrogen atmosphere, preferably a nitrogen atmosphere.
  3. 3. Cl-doped C of claim 23N5The method is characterized in that the mass ratio of the ammonium chloride to the 3-amino-1, 2, 4-triazole to the six-membered nitrogen heterocycle is 0.02-0.30: 1: 1.1-1.45; preferably, the hexa-membered nitrogen heterocycle is cyanuric acid and barbituric acid, and the mass ratio of the cyanuric acid to the barbituric acid is 1:0.1 to 0.45.
  4. 4. The Cl-doped C of claim 2 or 33N5The method is characterized by also comprising the step b of adding the fully and uniformly mixed powder obtained in the step a into an auxiliary agent solution, stirring, drying and then carrying out the step b on the dried powder; the auxiliary agent is potassium salt; the potassium salt is preferably at least one of potassium bromide, potassium chloride or potassium iodide, and the mass ratio of the auxiliary agent to the uniformly mixed powder is preferably 0-4%.
  5. 5. Cl-doped C according to claim 1 or 23N5Characterized in that said Cl-doped C3N5The band gap value of (A) is 1.16-1.22 eV, preferably 1.16 eV.
  6. 6. Cl-doped C according to any one of claims 1 to 53N5Its special featureCharacterized in that said Cl is doped with C3N5Has a specific surface area of 3.24m2/g～11.23m2/g。
  7. Cl-doped C3N5The method for producing (a), characterized by comprising:
    a. mixing materials: fully and uniformly mixing ammonium chloride, 3-amino-1, 2, 4-triazole and six-membered nitrogen heterocycle to obtain uniformly mixed powder, wherein the six-membered nitrogen heterocycle is at least one of cyanuric acid and barbituric acid;
    b. and (3) calcining: heating the uniformly mixed powder, preserving heat for more than 1.5 hours at 500-550 ℃, preferably preserving heat for 2-4 hours, cooling, taking out, washing and drying to obtain Cl-doped C3N5The calcination is carried out in an air or nitrogen atmosphere, preferably a nitrogen atmosphere.
  8. 8. Cl-doped C of claim 73N5The preparation method is characterized in that the mass ratio of the ammonium chloride to the 3-amino-1, 2, 4-triazole to the six-membered nitrogen heterocycle is 0.02-0.30: 1: 1.1-1.45; preferably, the hexa-membered nitrogen heterocycle is cyanuric acid and barbituric acid, and the mass ratio of the cyanuric acid to the barbituric acid is 1:0.1 to 0.45.
  9. 9. Cl-doped C according to claim 7 or 83N5The preparation method is characterized by further comprising the step b of adding the fully and uniformly mixed powder obtained in the step a into an auxiliary agent solution, stirring, drying and then carrying out the step b on the dried powder; the auxiliary agent is potassium salt; the potassium salt is at least one of potassium bromide, potassium chloride or potassium iodide, and the mass ratio of the auxiliary agent to the uniformly mixed powder is preferably 0-4%.
  10. 10. The Cl-doped C of claim 93N5The preparation method is characterized in that the stirring is performed for more than 1h at ambient temperature and then the ultrasound is performed for more than 1h at room temperature.
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