CN115400781A - Preparation method and application of two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst with enhanced n → pi-electron transition effect - Google Patents

Preparation method and application of two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst with enhanced n → pi-electron transition effect Download PDF

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CN115400781A
CN115400781A CN202211061045.0A CN202211061045A CN115400781A CN 115400781 A CN115400781 A CN 115400781A CN 202211061045 A CN202211061045 A CN 202211061045A CN 115400781 A CN115400781 A CN 115400781A
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carbon nitride
thiophene ring
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王帅军
贺凤婷
李斌
王贞涛
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Jiangsu University
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention belongs to the technical field of semiconductor photocatalysts, and discloses a preparation method and application of a two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst with an enhanced n → pi electron transition effect. The method comprises the following steps: adding urea and 2-aminothiophene-3-carbonitrile ATCN with different contents into water, stirring and copolymerizing, heating in a water bath to remove moisture, calcining in a muffle furnace, and naturally cooling and grinding to obtain carbon nitride grafted with thiophene rings; putting the catalyst with the optimal ATCN content into a porcelain boatCarrying out thermal hydrolysis calcination, naturally cooling the calcined product to obtain the two-dimensional carbon nitride nanosheet grafted with the thiophene ring, and marking as 2D Th ing -a CNNS photocatalyst. The grafted thiophene ring and the two-dimensional carbon nitride nanosheet can synergistically excite n → pi + electron transition, so that a pi conjugated system is expanded, interface charge transfer is accelerated, the specific surface area is increased, more active centers are provided for the reaction, and the effect of photocatalytic degradation of bisphenol A or water decomposition hydrogen production activity can be obviously enhanced.

Description

Preparation method and application of two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst with enhanced n → pi-electron transition effect
Technical Field
The invention belongs to the technical field of semiconductor photocatalysts, and particularly relates to a preparation method and application of a two-dimensional thiophene ring carbon nitride nanosheet photocatalyst with an enhanced n → pi electron transition effect.
Background
With the ever-increasing demand for energy and the excessive consumption of fossil fuels, serious energy crisis and environmental pollution problems have raised worldwide concern. Therefore, there is an urgent need to develop environmentally advanced materials and techniques to solve these problems. Semiconductor-mediated photocatalytic technology is considered a promising technology for its applications in hydrogen production, light-driven water decomposition, organic pollutant decomposition, and carbon dioxide abatement. The key issue of this technology depends to a large extent on the development of efficient materials. Polymeric carbon nitride (g-C) 3 N 4 ) As an excellent and inexpensive photocatalyst, attention has been paid to a series of excellent characteristics such as a simple synthesis, a suitable energy band structure (2.7 eV), and high physicochemical stability. However, g-C prepared by conventional methods 3 N 4 Due to low absorbance and slower charge separation and transfer efficiency, the photocatalytic degradation and water decomposition hydrogen production method is low in efficiency.
Recent researches show that n → pi electron transition induced by lone pair electrons in nitrogen atoms at the edge of triazine/heptazine ring of carbon nitride can enlarge delocalization of pi electrons, and effectively broaden g-C 3 N 4 The visible light responds to the wavelength material to 600nm, thereby effectively improving the photocatalytic performance of the material. However, g-C thus prepared 3 N 4 The performance of the photocatalyst is still to be further improved, and therefore, the n → π transition needs to be further strengthened to improve the photocatalytic performance.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon nitride photocatalyst for enhancing n → pi + electron transition aiming at some defects in the background technology, and to investigate the photocatalytic performance of the photocatalyst for photocatalytic degradation of bisphenol A wastewater and water decomposition to produce hydrogen under visible light. The method effectively maintains the excellent visible light absorption performance of the thiophene ring implanted carbon nitride, and simultaneously utilizes a method which is simple and convenient to operate, low in cost, green and pollution-free to further optimize the optical and electronic structure of the carbon nitride, accelerate the migration of photon-generated carriers, increase the specific surface area and improve the photocatalytic degradation of antibiotic wastewater and the hydrogen production performance by decomposing water.
In order to achieve the above object of the invention, the following technical solutions are adopted.
The preparation method of the two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst with the enhanced n → pi electron transition effect comprises the following steps of:
(1) Adding a certain amount of urea and 2-amino-3-cyanothiophene into water, stirring and copolymerizing, heating in a constant-temperature water bath to remove water, calcining in a muffle furnace, naturally cooling and grinding to obtain thiophene ring doped carbon nitride (denoted as X-Th) ing -CN; x is the mass percent of 2-amino-3-cyanothiophene and urea;
(2) The X-Th obtained in the step (1) ing Placing the-CN in a porcelain boat in a tube furnace, performing high-temperature pyrolysis in the nitrogen atmosphere, naturally cooling and grinding to obtain the thiophene ring doped two-dimensional carbon nitride nanosheet photocatalyst which is recorded as 2D Th ing -CNNS。
In the step (1), the dosage proportion of urea, 2-amino-3-cyanothiophene and water is 10-30g:5-100mg:10-30mL, X-Th ing in-CN, X is 0.016% -1%.
In the step (1), the temperature of the constant-temperature water bath is 50-80 ℃, and the time of the constant-temperature water bath is 5-7h.
In the step (1), the calcining temperature is 550-600 ℃, the heating rate is 5-15 ℃/min, and the calcining time is 2-6h.
In the step (2), the high-temperature re-pyrolysis temperature is 620-670 ℃, the heating rate is 5-10 ℃/min, and the time is 2-6h.
In the step (2), the porcelain boat is wrapped and sealed by tinfoil, so that the yield and the crystallinity of the catalyst are ensured.
The invention discloses application of a two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst with enhanced n → pi electron transition effect in photocatalytic degradation of phenols or decomposition of water to produce hydrogen.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a preparation method of a two-dimensional thiophene ring carbon nitride nanosheet photocatalyst with enhanced n → pi electron transition effect, which firstly proposes that on the basis of implanting a thiophene ring, n → pi electron transition is further enhanced through a high-temperature re-pyrolysis strategy to regulate and control g-C 3 N 4 The two-dimensional thiophene ring grafted g-C is prepared 3 N 4 Nanosheet (2 DTh) ing CNNS), implantation of a thiophene ring conferring g-C 3 N 4 The expanded pi conjugated system stimulates n → pi + electron transition and accelerates interface charge transfer; the two-dimensional nanosheet structure increases Th ing The specific surface area of the-CN material provides more active centers for reaction, and further enhances n → pi electron transition to create more transfer channels for photo-generated electrons; in addition, when the thiophene ring is implanted and a thermal hydrolysis strategy is combined, the positions of a conduction band and a valence band are obviously adjusted, and the transmission and the migration of photon-generated carriers are obviously improved. Make 2D Th ing The CNNS photocatalyst has more efficient photocatalytic activity. Has wide application prospect in the fields of environmental pollution control, energy sources and the like.
(2) The invention provides a 2D Th ing -CNNS photocatalyst, comparable to conventional g-C 3 N 4 The method has the advantages of obviously enhanced activity of photocatalytic degradation of bisphenol A wastewater and decomposition of hydrogen in water, obviously widened light absorption range of visible light, obviously increased n → pi + electron transition, simple and convenient operation of the preparation method, easy operation and environmental friendliness.
Drawings
FIG. 1 shows the 2D Th prepared by the present invention ing -a schematic flow diagram for the preparation of CNNS photocatalysts;
FIG. 2 is g-C prepared in comparative example 1 3 N 4 And example 1 preparation2D Th ing -transmission electron microscopy of CNNS photocatalyst;
FIG. 3 is a graph of g-C prepared in comparative examples 1-2 3 N 4 2D CNNS, X% -Th of example 1 ing -CN and 2DTh ing -X-ray diffraction pattern of CNNS photocatalyst;
FIG. 4 is a graph of g-C prepared in comparative examples 1-2 3 N 4 2D CNNS, X% -Th of example 1 ing -CN and 2DTh ing -a uv-vis diffuse reflectance spectrum of a CNNS photocatalyst;
FIG. 5 is a graph of g-C prepared in comparative examples 1-2 3 N 4 2D CNNS, 0.10% -Th of example 1 ing -CN and 2DTh ing -photoluminescence spectrum of CNNS photocatalyst;
FIG. 6 is a graph of g-C prepared in comparative examples 1-2 3 N 4 2D CNNS, 0.10% -Th of example 1 ing -CN and 2DTh ing -electron spin resonance spectrum of CNNS photocatalyst;
FIG. 7 is a graph of g-C prepared in comparative examples 1-2 3 N 4 2D CNNS, 0.10% -Th of example 1 ing -CN and 2DTh ing -CNNS photocatalyst under visible light (λ)>420 nm) on the graph of the photocatalytic degradation rate of BPA wastewater;
FIG. 8 is a graph of g-C prepared in comparative examples 1-2 3 N 4 2D CNNS, 0.10% -Th of example 1 ing -CN and 2DTh ing -CNNS photocatalyst under visible light (λ)>420 nm) to decompose water to produce hydrogen.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. However, it should not be construed as limiting the invention. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Comparative example 1:
g-C 3 N 4 preparation of the photocatalyst:
weighing 10g of urea in a closed crucible, placing the closed crucible in a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, calcining for 2h,naturally cooling to room temperature after calcination to obtain g-C 3 N 4 。
Comparative example 2:
preparation of 2D CNNS photocatalyst:
weighing 300mg g-C 3 N 4 Placing the mixture in an open corundum porcelain boat, placing the open corundum porcelain boat in a tube furnace, heating the mixture to 620 ℃ at the heating rate of 5 ℃/min, calcining the mixture for 2 hours, and naturally cooling the calcined mixture to room temperature to obtain the 2D CNNS.
Example 1
(1)X-Th ing -preparation of CN photocatalyst:
adding 10g of urea and ATCN with different contents (5, 10,30,50, 100mg) into 10mL of water, stirring for 12h, heating in a water bath at 80 ℃ to evaporate water, placing in a crucible, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h, naturally cooling after calcining, and grinding to obtain X-Th ing -CN. (X =0.05%, 0.10%, 0.30%, 0.50%, and 1.00%)
(2)2D Th ing -preparation of CNNS photocatalyst:
weighing 300mg 0.1% -Th ing Placing CNNS in an open corundum porcelain boat, placing in a tube furnace, heating to 620 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, calcining for 2h, and naturally cooling to room temperature after calcining to obtain 2DTh ing -CNNS；
Example 2
(1)X-Th ing -preparation of CN photocatalyst:
adding 20g of urea and ATCN with different contents (5, 10,30,50 and 100 mg) into 20mL of water, stirring for 12h, heating in a water bath at 80 ℃ to evaporate water, placing in a crucible, heating to 550 ℃ at a heating rate of 10 ℃/min, calcining for 4h, naturally cooling after calcining, and grinding to obtain X-Th ing -CN. (X =0.025%, 0.05%, 0.15%, 0.25%, and 0.5%)
(2)2D Th ing Preparation of CNNS photocatalyst:
600mg 0.05% -Th is weighed ing CNNS in open corundum porcelain boat and in tube furnace under nitrogenHeating to 650 ℃ at a heating rate of 5 ℃/min in a gas atmosphere, calcining for 2h, and naturally cooling to room temperature after the calcination is finished to obtain 2DTh ing -CNNS。
Example 3
(1)X-Th ing -preparation of CN photocatalyst:
adding 30g of urea and ATCN with different contents (5, 10,30,50 and 100mg) into 30mL of water, stirring for 12h, heating in a water bath at 80 ℃ to evaporate water, then placing in a crucible in a muffle furnace, heating to 550 ℃ at a heating rate of 15 ℃/min, calcining for 6h, naturally cooling after calcining, and grinding to obtain X-Th ing -CN. (X =0.017%, 0.033%, 0.10%, 0.17% and 0.33%)
(2)2D Th ing Preparation of CNNS photocatalyst:
weighing 900mg 0.033% -Th ing Placing CNNS in an open corundum porcelain boat, placing in a tube furnace, heating to 670 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, calcining for 2h, and naturally cooling to room temperature after the calcination is finished to obtain 2DTh ing -CNNS。
2D Th prepared as in example 1 ing CNNS carries out subsequent performance tests:
experimental procedure for photocatalytic degradation of bisphenol A (BPA):
25mg of 2D Th photocatalyst powder prepared in example 1 were weighed ing CNNS was added to a 50mL solution containing BPA at a concentration of 10mg/L. Before the photoreaction, the mixture was stirred in the dark for 1 hour to reach the adsorption-desorption equilibrium. Then, the photoreaction was performed while maintaining the temperature at room temperature. After the light source was turned on, 1.5mL of the solution was taken at given time intervals, and after filtering the photocatalyst powder using a 0.22 μm microporous filter, the BPA concentration was measured using an HPLC C18 column and a UV detector (SPD-20A, japan) at a mobile phase volume ratio of methanol: water (60 -1 The chromatographic column is a C18 separation column at the temperature of 30 ℃.
The experimental process of photocatalytic water splitting hydrogen production:
weighing 25mg of the prepared 2D Th ing Addition of CNNS photocatalyst powder to a solution containing 10vol.% triethanolamine and 3In wt.% Pt in water (25 mL), it was dispersed homogeneously by sonication for 30 min. Prior to the reaction, the reactor was degassed by pulling a vacuum to remove air dissolved in water. The temperature of the reactor was maintained at 6 ℃ by the fluidity of the cooling circulation water. Irradiation with a 300W xenon lamp stabilized light source equipped with a 420nm cut-off filter with N 2 As carrier gas, a thermal conductivity detector and
Figure BDA0003826190450000051
the molecular sieve column was used for on-line gas chromatography analysis of the liberated hydrogen.
g-C of comparative example 1 3 N 4 2D CNNS of comparative example 2, 0.1% -Th of example 1 ing CNNS adopts the same method to examine the hydrogen production performance of degrading bisphenol A and decomposing water by photocatalysis.
FIG. 1 is a 2D Th ing -synthetic process diagram of CNNS. 2D Th ing the-CNNS can be obtained by two steps of copolymerization and high-temperature thermal pyrolysis.
FIGS. 2a and b are g-C, respectively 3 N 4 And 2D Th ing -transmission electron microscopy images of CNNS. g-C 3 N 4 Exhibit an irregular dense lamellar structure, while 2D Th ing The CNNS presents a porous loosely pleated nanosheet texture, which not only helps to retain the easier activation of intrinsic pi → pi @, but can also activate g-C 3 N 4 N → pi.
FIG. 3 is g-C 3 N 4 、2D CNNS、X-Th ing -CN and 2D Th ing -X-ray diffraction pattern of CNNS. g-C 3 N 4 And X-Th ing The — CN exhibited two main peaks at approximately 13.1 ° and 27.2 °, corresponding to the in-plane periodic stacking of (001) heptazine units and (002) aromatic interlayer stacking, respectively. X-Th ing The widths of the two characteristic peaks of the-CN broaden with increasing ATCN content, mainly due to graphite stacking and irregular Th ing The interference caused by the entrance plane reduces the structural order. In contrast, 2D CNNS and 2D Th ing The two peaks of CNNS became narrower and sharper than the other samples, indicating that their crystal structures developed wellGood and coherent. In addition, 2D CNNS and 2D Th ing The peak of-CNNS is slightly shifted to 27.7 °, corresponding to a layer spacing from 0.327nm to 0.322nm, indicating a reduction in layer spacing, which may be attributed to the enhanced van der waals attraction between the heptazine layer interactions. In addition, the peak corresponding to the (001) crystal plane is shifted from 13.1 ° to 12.8 °, the in-plane distance is extended from 0.675nm to 0.693nm, and the stacking distance of the extended crystal plane can break the hydrogen bond and distort the planar symmetric structural unit of triazine, thereby creating conditions for realizing n → π × transition.
FIG. 4 shows g-C 3 N 4 、2D CNNS、X-Th ing -CN and 2D Th ing UV-VIS absorption spectrum of CNNS. g-C 3 N 4 Showing an absorption edge around 460 nm. In contrast, X-Th ing the-CN sample shows obviously different visible light photoresponse, and the X-Th is increased along with the increase of the ATCN content ing The absorption edge of-CN gradually red shifts to the near infrared region (from 650nm to over 900 nm) and a new absorption peak appears at about 500nm, which is associated with the n → pi transition. This phenomenon indicates that the incorporation of the thiophene ring destroys the original g-C 3 N 4 Structure, an asymmetric planar structure is produced. The same phenomenon also occurs in 2D CNNS and 2D Th ing In CNNS, it is shown that high temperature thermal hydrolysis can also deform the structure, inducing n → π transition. Furthermore, with 0.10% -Th ing 2DTh, comparable to-CN ing CNNS further expands the light absorption edge and enhances the ability of n → pi transition. These results indicate that implantation of a thiophene ring in combination with a reheat hydrolysis strategy can synergistically promote n → pi electron transitions.
FIG. 5 is g-C 3 N 4 、2D CNNS、X-Th ing -CN and 2D Th ing Photoluminescence spectrum of CNNS. 0.10% -Th ing -CN and 2D Th ing -CNNS vs g-C 3 N 4 And 2D CNNS showed significant fluorescence quenching and red-shift, which may be caused by the extension of the conjugated system of π electrons. The results indicate that the grafted thiophene ring can effectively inhibit the recombination photoinduced carriers. Notably, g-C 3 N 4 Only one emission peak is shown in the PL spectrum, which results from pi → in the conjugated systemPi transition. But for 2D CNNS, 0.10% -Th ing -CN and 2D Th ing The CNNS shows another new peak, which is assigned to the n → π electron transition.
FIG. 6 shows g-C 3 N 4 、2D CNNS、X-Th ing -CN and 2D Th ing Electron Paramagnetic Resonance (EPR) spectra of CNNS, which also indirectly confirmed the occurrence of n → π transitions. As can be seen, the prepared material shows a clear Lorentz line centered at a g value of 2.0592, which is related to unpaired electrons in the π conjugated aromatic ring. The relevant literature reports that the n → pi electron transition excites more non-bonding electrons in the catalyst. And g-C 3 N 4 2D CNNS with n → π electron transition, 0.10% -Th with slightly enhanced EPR intensity ing -CN and 2D Th ing CNNS exhibits a larger enhanced signal span, indicating the presence of more unpaired electrons.
FIG. 7 is g-C 3 N 4 、2D CNNS、0.10％-Th ing -CN and 2D Th ing Graph of photocatalytic degradation rate of bisphenol a (BPA) wastewater by CNNS under visible light. As shown in FIG. 7, g-C was observed within 40min of visible light irradiation 3 N 4 The degradation reaction is slow, and the degradation rate only reaches 6.1 percent. In contrast, 2D Th ing The degradation performance of the-CNNS is obviously improved, the degradation rate of TC reaches 100 percent, and 2D Th is improved ing The improvement of CNNS performance is due to increased visible light absorption, fast charge separation efficiency and increased specific surface area.
FIG. 8 is g-C 3 N 4 、2D CNNS、0.10％-Th ing -CN and 2D Th ing A graph of the rate of hydrogen production by CNNS decomposition of water under visible light. As shown, 2D Th ing The average photocatalytic hydrogen production rate of CNNS is 11785 mu mol h -1 g -1 Specific g-C 3 N 4 (1031μmol h -1 g -1 ) The improvement is 11.4 times. Further, 2D Th ing CNNS also showed a comparison with 2D CNNS (5714. Mu. Mol h) -1 g -1 ) And 0.10% -Th ing -CN(7760μmol h -1 g -1 ) Much higher photocatalytic activity. The enhanced photocatalytic performance is attributable to enhanced n → pi electron transitions and twoThe nano-sheet structure provides more active sites and facilitates charge separation.
It should be noted that the above-described embodiments may enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way. Thus, it will be understood by those skilled in the art that the present invention may be modified and equivalents may be substituted; all technical solutions and modifications thereof which do not depart from the spirit and technical essence of the present invention should be covered by the scope of the present patent.

Claims (8)

1. The preparation method of the two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst with the enhanced n → pi electron transition effect is characterized by comprising the following steps of:
(1) Adding a certain amount of urea and 2-amino-3-cyanothiophene into water, stirring and copolymerizing, heating in a constant-temperature water bath to remove water, calcining in a muffle furnace, naturally cooling and grinding to obtain thiophene ring doped carbon nitride (denoted as X-Th) ing -CN; x is the mass percent of 2-amino-3-cyanothiophene and urea;
(2) The X-Th obtained in the step (1) ing Placing the-CN in a porcelain boat in a tube furnace, performing high-temperature pyrolysis in the nitrogen atmosphere, naturally cooling and grinding to obtain the thiophene ring doped two-dimensional carbon nitride nanosheet photocatalyst which is recorded as 2D Th ing -CNNS。
2. The process according to claim 1, wherein in the step (1), the urea, the 2-amino-3-cyanothiophene and the water are used in a ratio of 10 to 30g:5-100mg:10-30mL, X-Th ing in-CN, X is 0.016% -1%.
3. The preparation method according to claim 1, wherein in the step (1), the temperature of the thermostatic water bath is 50-80 ℃ and the time of the thermostatic water bath is 5-7h.
4. The preparation method according to claim 1, wherein in the step (1), the calcination temperature is 550-600 ℃, the temperature rise rate is 5-15 ℃/min, and the calcination time is 2-6h.
5. The preparation method according to claim 1, wherein in the step (2), the high-temperature re-pyrolysis temperature is 620-670 ℃, the temperature rise rate is 5-10 ℃/min, and the time is 2-6h.
6. The method of claim 1, wherein in the step (2), the porcelain boat is wrapped with tinfoil in a sealed state to ensure the yield and crystallinity of the catalyst.
7. Use of the two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst having enhanced n → pi electron transition effect prepared according to any one of claims 1 to 6 in the photocatalytic degradation of phenols.
8. Use of the two-dimensional thiophene ring-doped carbon nitride nanosheet photocatalyst having an enhanced n → pi x electron transition effect prepared according to any one of claims 1 to 6 in the production of hydrogen by decomposition of water.
CN202211061045.0A 2022-09-01 2022-09-01 Preparation method and application of two-dimensional thiophene ring doped carbon nitride nanosheet photocatalyst with enhanced n → pi-electron transition effect Pending CN115400781A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116273162A (en) * 2023-03-01 2023-06-23 安徽工程大学 Composite photocatalytic material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471711A (en) * 2022-01-24 2022-05-13 华南理工大学 Polythiophene-carbon nitride composite photocatalyst and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114471711A (en) * 2022-01-24 2022-05-13 华南理工大学 Polythiophene-carbon nitride composite photocatalyst and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FENGTING HE等: "Manipulation of n→π* electronic transitions via implanting thiophene rings into two-dimensional carbon nitride nanosheets for efficient photocatalytic water purification", 《JOURNAL OF MATERIALS CHEMISTRY A》, pages 20559 *
李雪 等: "噻吩环掺杂氮化碳纳米片的制备及光催化性能", 《无机化学学报》, vol. 38, no. 4, pages 654 - 664 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116273162A (en) * 2023-03-01 2023-06-23 安徽工程大学 Composite photocatalytic material and preparation method thereof
CN116273162B (en) * 2023-03-01 2023-09-05 安徽工程大学 Composite photocatalytic material and preparation method thereof

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