CN117884161A - Nonmetal-doped graphite-phase carbon nitride and preparation method and application thereof - Google Patents
Nonmetal-doped graphite-phase carbon nitride and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses nonmetal-doped graphite-phase carbon nitride, a preparation method and application thereof, and belongs to the technical fields of organic nanomaterials and photocatalysis. The preparation method of the nonmetallic doped graphite phase carbon nitride comprises the following steps: calcining the nitrogen-containing organic matter at 500-600 ℃ in the atmosphere of protective gas to obtain a catalyst; mixing a catalyst with a nonmetallic compound to obtain a mixture; calcining the mixture at 360-450 ℃ in the atmosphere of protective gas to obtain the nonmetallic doped graphite phase carbon nitride. The nonmetal-doped graphite phase carbon nitride prepared by the method has high-efficiency visible light catalytic activity and can realize hydrogen peroxide production.
Description
Technical Field
The invention relates to the technical field of organic nano materials and photocatalysis, in particular to non-metal doped graphite phase carbon nitride, a preparation method and application thereof.
Background
Aiming at the removal of organic pollutants in water, mainly coagulation, activated carbon filtration, biological filtration, advanced oxidation and the like, wherein Fenton and Fenton-like reaction can effectively remove various organic compounds by using a powerful oxidant, and the most common degradation method in industry at present is to degrade the organic pollutants in water by generating hydrogen peroxide. The production of hydrogen peroxide is highly dependent on indirect anthraquinone oxidation, alcohol oxidation or direct synthesis from hydrogen and oxygen, but this is a wasteful, energy-consuming and explosive process. Therefore, it is important to develop a method for degrading organic pollutants in water by efficiently and environmentally producing hydrogen peroxide. Photocatalytic technology has been widely used as a novel cleaning technology in terms of organic pollutant degradation, and the production of hydrogen peroxide driven by solar energy is considered a promising strategy due to its safety, sustainability, economy, energy conservation and environmental protection properties. However, the most advanced artificial photocatalysis hydrogen peroxide production process still does not reach ideal efficiency due to the low yield of the required active oxygen, strong side reaction competitiveness and the like, and the preferred alternative scheme for efficiently producing hydrogen peroxide is to improve the efficient production of the required active oxygen and inhibit the side reaction.
The performance of graphite-phase carbon nitride as a semiconductor material in catalysis is not found until 2006, and the application of graphite-phase carbon nitride in heterogeneous catalysis is started in 2006, and the group of professor Wang Xinchen of Fuzhou university confirms in 2009 that a graphite-phase carbon nitride nonmetallic semiconductor can catalyze water to generate hydrogen under illumination, and is a photocatalytic material which is found in the photocatalytic field and has visible light response. Compared with the traditional titanium dioxide photocatalyst, the graphite phase carbon nitride has wider absorption spectrum range, and can play a role in photocatalysis under common visible light without ultraviolet light; meanwhile, compared with titanium dioxide, the graphite phase carbon nitride can more effectively activate molecular oxygen, and generates superoxide radicals for photocatalytic conversion of organic functional groups and photocatalytic degradation of organic pollutants, and is more suitable for degradation of organic matters.
Compared with the traditional photocatalyst titanium dioxide, the graphite phase carbon nitride can absorb visible light to generate electrons and holes, but has a slightly wider band gap, and has lower utilization degree of the visible light. How to enhance the utilization of visible light and reduce exciton binding energy has become the research direction for many scholars.
There have been studies today that the absorption of visible light can be enhanced, generally by doping to change the conduction band, valence band position and band gap width. Chang et al (Enhancing Light-Driven Production of Hydrogen Pero xide by Anchoring Au onto C3N4 Catalysts.Catalysts.2018,8:147) report a gold-doped graphite phase carbon nitride, however the materials used in the above report are noble metals, expensive, and unsuitable for large-scale applications. Ma et al (Photocatalysis-Self-Fenton System with High-Fluent Degradation and High Mineralization Ability,Applied Catalysis B:Environme ntal.2020,276:119150) report a phosphorus doped graphite-based carbon nitride material, but the hydrogen peroxide generating capability of the above-mentioned research materials has yet to be improved. Through searching, the Chinese patent invention relates to the preparation and application of graphite-phase doped carbon nitride, for example: ag (silver) -doped carbon nitride/P (phosphorus) -doped carbon nitride Z-type homojunction photocatalyst, and preparation method and application thereof (application number: 202310221817.0); the preparation method of the cotton fiber loaded silver doped carbon nitride-titanium dioxide composite material (application number: 20201117290. X) mainly adopts a noble metal doping or homogeneous junction construction mode to modify graphite phase carbon nitride, has relatively complex operation steps and relatively high cost, and is not beneficial to large-scale application in actual production. Meanwhile, through searching, the research on hydrogen peroxide production by carbon nitride doped with graphite phase is rarely related to the domestic published patent.
Disclosure of Invention
Aiming at the problems, the invention provides the nonmetal-doped graphite-phase carbon nitride, and the preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In a first aspect, the invention provides a method for preparing nonmetallic doped graphite-phase carbon nitride, comprising the following steps:
calcining the nitrogen-containing organic matter at 500-600 ℃ in the atmosphere of protective gas to obtain a catalyst;
For example, the calcination temperature is 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃; however, the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
Mixing a catalyst with a nonmetallic compound to obtain a mixture;
calcining the mixture at 360-450 ℃ in the atmosphere of protective gas to obtain the nonmetallic doped graphite phase carbon nitride.
For example, the calcination temperature is 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃; however, the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
In one embodiment of the invention, the nitrogen-containing organic matter is one or more of cyanamide, dicyandiamide and melamine.
Typical, but non-limiting examples of such combinations include combinations of cyanamide and dicyandiamide, combinations of dicyandiamide and melamine, combinations of dicyandiamide, melamine and cyanamide, and the like.
In one embodiment of the invention, the calcination time of the nitrogen-containing organic matter is 4-6 hours, e.g., 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, etc.;
The heating rate is 2.5 to 5℃per minute, for example, 2.5℃per minute, 3℃per minute, 3.5℃per minute, 4℃per minute, 4.5℃per minute, 5℃per minute, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned ranges are applicable.
In one embodiment of the present invention, the nonmetallic in the nonmetallic compound is one or more of boron, sulfur, nitrogen, and phosphorus.
Typical, but non-limiting examples of such combinations include combinations of boron and sulfur, combinations of boron and nitrogen, combinations of boron and phosphorus, combinations of sulfur and nitrogen, combinations of sulfur and phosphorus, combinations of nitrogen and phosphorus, combinations of sulfur, nitrogen and phosphorus, and the like.
In one embodiment of the invention, the mixing is a milling mixing for a period of 0.5 to 3 hours.
For example, the polishing time is 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, etc., but the polishing time is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
In one embodiment of the invention, the mass ratio of catalyst to nonmetallic compound is 1:2-10.
For example, the mass ratio of catalyst to nonmetallic compound is 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., but is not limited to the recited values, and other non-recited values within the above-recited ranges are equally applicable.
In one embodiment of the invention, the mixture is calcined for a time of 2-5 hours, e.g., 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, etc.;
The temperature rising rate is 2.5-5 ℃/min. For example, the heating rate is 2.5℃per minute, 3℃per minute, 3.5℃per minute, 4℃per minute, 4.5℃per minute, 5℃per minute, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value ranges are applicable.
In a second aspect, the present invention provides a non-metal doped graphite phase carbon nitride obtained by the method of the first aspect, the non-metal doped graphite phase carbon nitride being modified by non-metal doping and formation of nitrogen vacancies.
In a third aspect, the present invention provides the use of a non-metal doped graphite phase carbon nitride as described in the second aspect, the use comprising photocatalytic production of hydrogen peroxide.
In one embodiment of the invention, visible light is used as a light source, an alcohol substance is used as a sacrificial agent, nonmetallic doped graphite phase carbon nitride is added, the pH is adjusted to 1-9, and oxygen is introduced to prepare the hydrogen peroxide.
The pH is 1,2,3, 4, 5, 6, 7, 8, 9, etc., but is not limited to the values recited, and other values not recited in the above-mentioned ranges are equally applicable.
Compared with the prior art, the invention has the following beneficial effects:
the present invention prepares a non-metal doped graphite phase carbon nitride in which the non-metal exists in a form of being combined with nitrogen vacancies. Compared with the prior art, the modified carbon nitride obviously reduces exciton effect through nonmetal doping and formation of nitrogen vacancy modified carbon nitride, has high-efficiency visible light catalytic activity, can realize the reduction of double-electron oxygen to produce hydrogen peroxide, has the yield of 23.3 mmol.L -1·g-1·h-1, and has the reduction selectivity of the double-electron oxygen of 100 percent. The non-metal content of the modified carbon nitride is 0.1-1 wt%, the nitrogen-carbon ratio is reduced by 2-5%, and the maximum absorption wavelength of the spectrum is 400-800 nm.
The synthesis method provided by the invention is simple in technological operation, and the prepared nonmetallic doped graphite-phase carbon nitride can spontaneously promote the adsorption and activation of oxygen and the desorption of hydrogen peroxide, so that the nonmetallic doped graphite-phase carbon nitride has high-efficiency photocatalytic performance. The high visible light response nonmetal doped carbon nitride prepared by the invention can fully utilize visible light and natural photocatalysis to generate clean energy, degrade toxic and harmful organic matters in the environment, resist bacteria, deodorize and other environmental protection industries.
Drawings
FIG. 1 is a XPS full spectrum (a) of carbon nitride prepared in comparative example 1 and non-metal doped graphite phase carbon nitride prepared in example 2 and a B1s spectrum (B) of non-metal doped graphite phase carbon nitride prepared in example 2;
FIG. 2 is an EPR spectra of carbon nitride prepared in comparative example 1 and non-metal doped carbon nitride prepared in example 2;
FIG. 3 is a TEM image of the carbon nitride (a) prepared in comparative example 1 and the nonmetallic doped carbon nitride (b) prepared in example 2;
FIG. 4 is a graph comparing the formation of hydrogen peroxide from carbon nitride prepared in comparative example 1 and non-metal doped carbon nitride prepared in example 2;
FIG. 5 is a graph of the degradation rate of 4-nitrophenol by in situ degradation of non-metal doped carbon nitride generated hydrogen peroxide prepared in example 2;
FIG. 6 is a graph comparing hydrogen peroxide generated by non-metal doped carbon nitride prepared in comparative example 1 with that generated by non-metal doped carbon nitride prepared in example 2 for the degradation of 4-nitrophenol.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present invention, "one or more" means any one, any two or more of the listed items. Wherein "several" means any two or more.
In the present invention, the terms "first", "second", "third", "fourth", "first", "second", "first section", "second section", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity or as implicitly indicating the importance or quantity of a technical feature indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
In the present invention, the numerical range is referred to, and both ends of the numerical range are included unless otherwise specified.
In the prior art, although carbon nitride is prepared, most of the prepared carbon nitride is directly applied to pollutant degradation and hydrogen production and oxygen production, and rarely relates to hydrogen peroxide production.
Based on the method, the prepared nonmetallic doped graphite-phase carbon nitride can be used for producing hydrogen peroxide and the like. The specific technical scheme is as follows:
the preparation method comprises the following steps:
step 1, calcining a nitrogenous organic substance at 500-600 ℃ in a protective gas atmosphere to obtain a catalyst;
Step 2, mixing a catalyst with a nonmetallic compound to obtain a mixture;
and 3, calcining the mixture at 360-450 ℃ in a protective gas atmosphere to obtain the nonmetallic doped graphite phase carbon nitride.
The invention adopts organic nitrogen substances as raw materials, the raw materials are placed in a ceramic crucible, the ceramic crucible is placed in a tube furnace for heating and calcining, the obtained product is ground and mixed with a nonmetallic compound, the mixture is placed in the tube furnace for heating and calcining, and nonmetallic doped graphite phase carbon nitride is realized through the control of reaction raw materials, reaction procedures and reaction conditions.
The high visible light response nonmetal-doped graphite phase carbon nitride prepared by the invention is modified by nonmetal doping and forming nitrogen vacancies, wherein the formation of the nitrogen vacancies is caused by hydrogen bond fracture of a polymerization unit or heat-driven release of amino groups in calcination to introduce some nitrogen anion vacancies in the structure of the carbon nitride.
Compared with the prior art, the modified carbon nitride obviously reduces the exciton effect, has high-efficiency visible light catalytic activity, can realize the dual-electron oxygen reduction to produce hydrogen peroxide, has the yield of 23.3 mmol.L -1·g-1·h-1, and has the dual-electron oxygen reduction selectivity of 100 percent. The non-metal content of the modified carbon nitride is 0.1-1 wt%, the nitrogen-carbon ratio is reduced by 2-5%, and the maximum absorption wavelength of the spectrum is 400-800 nm.
In one embodiment of the invention, the nitrogen-containing organic matter is one or more of cyanamide, dicyandiamide and melamine.
In one embodiment of the invention, the calcination time of the nitrogen-containing organic matter is 4-6 hours, and the temperature rising rate is 2.5-5 ℃/min.
In the calcination process, the structure of the catalyst burnt out with longer calcination time may be different, if the temperature is too low and the time is too short, the polymerization is insufficient, the performance of catalyzing and producing hydrogen peroxide is poor, the hydrogen peroxide yield is low, and the pollutant degradation effect is poor. Similarly, too high a temperature or too long a time, the performance of catalyzing hydrogen peroxide production is poor, and the effect of degrading pollutants is poor.
In one embodiment of the present invention, the nonmetallic in the nonmetallic compound is one or more of boron, sulfur, nitrogen, and phosphorus.
The non-metal compound containing boron is boric acid, sodium tetraborate, etc.;
the nonmetallic compounds containing phosphorus are ammonium phosphate, hexachloro-triphosphazene, thiourea and the like;
the nonmetallic compounds containing sulfur are molybdenum disulfide, sodium thiosulfate and the like;
The nonmetallic compounds containing nitrogen are urea and the like.
In one embodiment of the invention, the mixing is a milling mixing for a period of 0.5 to 3 hours.
In one embodiment of the invention, the mass ratio of catalyst A to the nonmetallic compound is 1:2-10.
In one embodiment of the invention, the calcination time of mixture B is 2-5 hours and the temperature rise rate is 2.5-5 ℃/min.
The graphite-phase carbon nitride disclosed in the prior art is mostly used for direct pollutant degradation and hydrogen, oxygen and methane production. For example, when hydrogen and methane are produced, the required catalyst generally needs to have the advantages of high charge separation degree, less recombination, easy separation and the like, but when hydrogen peroxide is produced, the problems of exciton effect, oxygen reduction, water oxidation capacity and the like of the catalyst need to be considered, and the problem that the hydrogen peroxide can be produced can solve the limitations of more secondary pollutants, difficult transportation, unsafe and the like in the existing industrial hydrogen peroxide production process. The design of catalysts for hydrogen production and methane and hydrogen peroxide production are not the same starting point, and therefore, it is desirable to provide a catalyst for hydrogen peroxide production.
Therefore, the invention provides the nonmetal-doped graphite-phase carbon nitride based on hydrogen peroxide production, which can be applied to photocatalysis preparation of hydrogen peroxide, and the prepared hydrogen peroxide is utilized to degrade pollutants in wastewater and realize antibacterial deodorization.
By taking non-metal boron doping as an example, when the graphite phase carbon nitride is prepared, the boron-nitrogen vacancy (B-N V) association is introduced into the carbon nitride, so that the strong exciton effect can be weakened, and the self-dissociation of bound excitons into free carriers under the environmental condition is promoted. Specifically, the doped boron atoms introduce a donor state under the conduction band of the carbon nitride, disrupting the charge distribution around the heptazine ring, further destabilizing the exciton. The accompanying nitrogen vacancies act as acceptor states above the valence band, forming B-N V associations in concert with the doped boron atoms, while lowering the conduction and valence bands of the carbon nitride. Unlike the tendency to activate oxygen to singlet oxygen by the energy transfer pathway, carbon nitride with B-N V associates exhibits superior photocatalytic activity in a visible light driven two electron oxygen reduction reaction. And the generated hydrogen peroxide can be applied in situ, such as degradation of pollutants (rhodamine B and 4-nitrophenol), sterilization, disinfection and the like. Similarly, when the doped nonmetal is sulfur, phosphorus or nitrogen, the photocatalytic performance of the graphite phase carbon nitride is improved by the improvement of the concentration of free carriers.
The various materials or reagents used in the examples of the present invention are not particularly limited in source, and are conventional products commercially available. The preparation may also be carried out according to conventional methods known to the person skilled in the art.
Example 1
Step 1, placing 2g of melamine in a ceramic crucible, transferring the ceramic crucible into a tube furnace in nitrogen atmosphere, heating to 500 ℃ at a heating rate of 2.5 ℃/min, calcining, and keeping at constant temperature for 6 hours to obtain graphite-phase carbon nitride;
step 2, mixing 0.5g of graphite phase carbon nitride with 1g of sodium tetraborate according to a mass ratio of 1:2, and fully grinding for 1h to obtain a mixture;
step 3, transferring the mixture into a nitrogen atmosphere tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min, calcining, and keeping the constant temperature for 5 hours; cooling the obtained solid to room temperature, repeatedly filtering and washing the product by using hot water at 90 ℃ and absolute ethyl alcohol, and drying for 24 hours at 50 ℃ to obtain the high visible light response nonmetallic doped graphite phase carbon nitride.
Example 2
Step 1, placing 2g of melamine in a ceramic crucible, transferring the ceramic crucible into a nitrogen atmosphere tube furnace, heating to 550 ℃ at a heating rate of 2.5 ℃/min, calcining, and keeping at constant temperature for 4 hours to obtain graphite-phase carbon nitride;
Step 2, mixing 0.5g of graphite phase carbon nitride with 2.5g of sodium tetraborate according to a mass ratio of 1:5, and fully grinding for 1.5h to obtain a mixture;
Step 3, transferring the mixture into a nitrogen atmosphere tube furnace, heating to 360 ℃ at a heating rate of 5 ℃/min, calcining and keeping the constant temperature for 2 hours; cooling the obtained solid to room temperature, repeatedly filtering and washing the product by using hot water at 100 ℃ and absolute ethyl alcohol, and drying for 12 hours at 60 ℃ to obtain the high visible light response nonmetallic doped graphite phase carbon nitride.
Example 3
Step 1, placing 2g of melamine in a ceramic crucible, transferring the ceramic crucible into a nitrogen atmosphere tube furnace, heating to 600 ℃ at a heating rate of 3 ℃/min, calcining, and keeping at constant temperature for 4 hours to obtain graphite-phase carbon nitride;
Step 2, mixing 0.5g of graphite phase carbon nitride with 4g of sodium tetraborate according to a mass ratio of 1:8, and fully grinding for 2 hours to obtain a mixture;
Step 3, transferring the mixture into a nitrogen atmosphere tube furnace, heating to 360 ℃ at a heating rate of 3 ℃/min, calcining and keeping the constant temperature for 3 hours; cooling the obtained solid to room temperature, repeatedly filtering and washing the product by using hot water at 60 ℃ and absolute ethyl alcohol, and drying for 12 hours at 70 ℃ to obtain the high visible light response nonmetallic doped graphite phase carbon nitride.
Example 4
Step 1, placing 2g of dicyandiamide in a ceramic crucible, transferring the ceramic crucible into a nitrogen atmosphere tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, calcining, and keeping at constant temperature for 5 hours to obtain graphite-phase carbon nitride;
Step 2, mixing 0.5g of graphite phase carbon nitride with 5g of sodium thiosulfate according to a mass ratio of 1:10, and fully grinding for 3 hours to obtain a mixture;
step 3, transferring the mixture into a nitrogen atmosphere tube furnace, heating to 450 ℃ at a heating rate of 2.5 ℃/min, calcining and keeping the constant temperature for 4 hours; cooling the obtained solid to room temperature, repeatedly filtering and washing the product by using hot water at 60 ℃ and absolute ethyl alcohol, and drying for 12 hours at 70 ℃ to obtain the high visible light response nonmetallic doped graphite phase carbon nitride.
Example 5
Step 1, placing 2g of cyanamide in a ceramic crucible, transferring the ceramic crucible into a nitrogen atmosphere tube furnace, heating to 500 ℃ at a heating rate of 4 ℃/min, calcining, and keeping at constant temperature for 4 hours to obtain graphite-phase carbon nitride;
Step 2, mixing 0.5g of graphite phase carbon nitride with 3g of non-metallic compound according to a mass ratio of 1:6, and fully grinding for 2 hours to obtain a mixture; in this step, the nonmetallic compound is composed of equal mass of hexachlorotriphosphazene and boric acid.
Step 3, transferring the mixture into a nitrogen atmosphere tube furnace, heating to 360 ℃ at a heating rate of 3 ℃/min, calcining and keeping the constant temperature for 4 hours; cooling the obtained solid to room temperature, repeatedly filtering and washing the product by using hot water at 60 ℃ and absolute ethyl alcohol, and drying for 12 hours at 70 ℃ to obtain the high visible light response nonmetallic doped graphite phase carbon nitride.
Example 6
Step 1, placing 2g of dicyandiamide in a ceramic crucible, transferring the ceramic crucible into a nitrogen atmosphere tube furnace, heating to 600 ℃ at a heating rate of 2.5 ℃/min, calcining, and keeping the constant temperature for 4 hours to obtain graphite-phase carbon nitride;
Step 2, mixing 0.5g of graphite phase carbon nitride with 1g of urea according to a mass ratio of 1:2, and fully grinding for 0.5h to obtain a mixture;
Step 3, transferring the mixture into a nitrogen atmosphere tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min, calcining, and keeping the constant temperature for 4 hours; cooling the obtained solid to room temperature, repeatedly filtering and washing the product by using hot water at 60 ℃ and absolute ethyl alcohol, and drying for 12 hours at 70 ℃ to obtain the high visible light response nonmetallic doped graphite phase carbon nitride.
Example 7
Step 1, uniformly mixing 2g of melamine and 2g of cyanamide, placing the mixture in a ceramic crucible, transferring the ceramic crucible into a nitrogen atmosphere tube furnace, heating to 600 ℃ at a heating rate of 2.5 ℃/min, calcining, and keeping the constant temperature for 4 hours to obtain graphite-phase carbon nitride;
step 2, mixing 0.5g of graphite phase carbon nitride with 1g of sodium tetraborate according to a mass ratio of 1:2, and fully grinding for 0.5h to obtain a mixture;
Step 3, transferring the mixture into a nitrogen atmosphere tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min, calcining, and keeping the constant temperature for 4 hours; cooling the obtained solid to room temperature, repeatedly filtering and washing the product by using hot water at 60 ℃ and absolute ethyl alcohol, and drying for 12 hours at 70 ℃ to obtain the high visible light response nonmetallic doped graphite phase carbon nitride.
Comparative example 1
Placing 2g of melamine in a ceramic crucible, transferring the ceramic crucible into a nitrogen atmosphere tube furnace, heating to 550 ℃ at a heating rate of 2.5 ℃/min, calcining and keeping the constant temperature for 4 hours to obtain graphite-phase carbon nitride;
Comparative example 2
Step 1, mixing 1g of melamine and 2.5g of sodium tetraborate according to a mass ratio of 1:2.5, and fully grinding for 1.5 hours to obtain a mixture;
And 2, placing the mixture in a ceramic crucible, transferring the ceramic crucible into a nitrogen atmosphere tube furnace, heating to 550 ℃ at a heating rate of 2.5 ℃/min, calcining, keeping the temperature for 4 hours, cooling to room temperature, repeatedly filtering and washing the product by using hot water at 100 ℃ and absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain the non-metal doped graphite phase carbon nitride.
It is to be noted that the ratio of melamine to sodium tetraborate in step 1 of comparative example 2 after conversion was substantially equal to the ratio of carbon nitride to sodium tetraborate in example 2, except that 0.5g of carbon nitride was produced by calcination under the same conditions as 1g of melamine alone.
FIG. 1a is a graph showing XPS full spectra of non-metal doped graphite phase carbon nitride prepared in example 2 and carbon nitride prepared in comparative example 1, which are not greatly different, but the peak of B1s is not detected in carbon nitride prepared in comparative example 1, whereas as can be seen from graph B of FIG. 1, non-metal doped graphite phase carbon nitride prepared in example 2 can detect the peak of B1s, the peak at 191.98eV is a typical N-B-N bond, and this result shows that boron is successfully incorporated into the crystal structure of graphite phase carbon nitride.
Fig. 2 is an EPR spectrum of the carbon nitride prepared in comparative example 1 and the non-metal doped carbon nitride prepared in example 2, and it can be seen from fig. 2 that the non-metal doped graphite phase carbon nitride prepared in example 2 (i.e., the modified carbon nitride in fig. 2) has stronger defects than the carbon nitride prepared in comparative example 1 (i.e., the carbon nitride in fig. 2), indicating that nitrogen vacancies are formed according to the preparation method of the present invention. The existence of nitrogen vacancies can improve the photocatalytic activity of the nonmetallic doped graphite phase carbon nitride.
Fig. 3 is a TEM image of the carbon nitride (a) prepared in comparative example 1 and the non-metal doped carbon nitride (b) prepared in example 2, and it can be seen from fig. 3 that the doping of boron and the presence of nitrogen vacancies do not significantly damage the morphology of the carbon nitride.
Performance tests were performed on non-metal doped graphite phase carbon nitrides prepared in the examples and comparative examples below.
(1) Testing of photocatalytic hydrogen peroxide production: the method comprises the steps of taking simulated visible light as a light source, adjusting through a light filter, adopting an alcohol substance as a sacrificial agent, adjusting the pH value to be between 1 and 9, introducing oxygen at intervals of 5 to 30min within 2 hours, sampling, measuring the absorbance of the sample at 551nm by adopting an N, N-Diethyl Phenylenediamine (DPD)/Peroxidase (POD) method, wherein the used instrument is a CEL-HXF300-T3 light source system, and the used instrument is a T-UV1900 type ultraviolet-visible spectrophotometer. The specific detection mode is as follows:
1.1 30mg of the non-metal doped graphite phase carbon nitride prepared in example 1 was placed in a mixture of 30ml of distilled water and 10ml of isopropanol, and the pH was adjusted to 6 using 1M sodium hydroxide and 1M perchloric acid. The mixed solution is placed under a light source with the wavelength more than 400nm, and oxygen is introduced at the flow rate of 0.1L/min. 2.0ml of the suspension was taken every 30min and the catalyst was filtered with a 0.22 μm filter head. The obtained filtrate was measured at 551nm by the N, N-diethylphenylenediamine (DPD)/Peroxidase (POD) method, and the result showed that 35.8 mmol.L -1·g-1 was produced by illumination with visible light for 150 min.
1.2A mixture of 30ml of distilled water and 10ml of isopropanol was placed in 30mg of non-metal-doped graphite-phase carbon nitride prepared in example 2, and the pH was adjusted to 3 using 1M sodium hydroxide and 1M perchloric acid. The mixed solution is placed under a light source with the wavelength more than 400nm, and oxygen is introduced at the flow rate of 0.2L/min. 1.5ml of the suspension was taken every 30min and filtered with a 0.22 μm filter head. The obtained filtrate was measured at 551nm by the N, N-diethylphenylenediamine (DPD)/Peroxidase (POD) method, and the result showed that the irradiation with visible light for 150min resulted in 41.3 mmol.L -1·g-1.
The efficiency of the non-metal doped graphite phase carbon nitride (i.e., the modified carbon nitride in fig. 4) prepared in example 2 to generate hydrogen peroxide under visible light is shown in fig. 4, and the amount of hydrogen peroxide generated by the carbon nitride prepared in comparative example 1 is 5.9mmol·l -1·g-1. It can be seen that the modified carbon nitride effect is significantly improved over carbon nitride.
1.3 30Mg of the non-metal doped graphite phase carbon nitride prepared in example 3 was placed in a mixture of 30ml of distilled water and 10ml of isopropanol, and the pH was adjusted to 9 using 1M sodium hydroxide and 1M perchloric acid. The mixed solution is placed under a light source with the wavelength more than 400nm, and oxygen is introduced at the flow rate of 0.2L/min. 2.0ml of the suspension was taken every 30min and the catalyst was filtered with a 0.22 μm filter head. The obtained filtrate was measured at 551nm by the N, N-diethylphenylenediamine (DPD)/Peroxidase (POD) method, and the result showed that 30.2 mmol.L -1·g-1 was produced by illumination with visible light for 150 min.
1.4 30Mg of the non-metal doped graphite phase carbon nitride prepared in example 4 was placed in a mixture of 30ml of distilled water and 10ml of isopropanol, and the pH was adjusted to 9 using 1M sodium hydroxide and 1M perchloric acid. The mixed solution is placed under a light source with the wavelength more than 400nm, and oxygen is introduced at the flow rate of 0.2L/min. 2.0ml of the suspension was taken every 30min and the catalyst was filtered with a 0.22 μm filter head. The obtained filtrate was measured at 551nm by the N, N-diethylphenylenediamine (DPD)/Peroxidase (POD) method, and the result showed that 26.5 mmol.L -1·g-1 was produced by illumination with visible light for 150 min.
1.5 30Mg of the non-metal doped graphite phase carbon nitride prepared in example 5 was placed in a mixture of 30ml of distilled water and 10ml of isopropanol, and the pH was adjusted to 9 using 1M sodium hydroxide and 1M perchloric acid. The mixed solution is placed under a light source with the wavelength more than 400nm, and oxygen is introduced at the flow rate of 0.2L/min. 2.0ml of the suspension was taken every 30min and the catalyst was filtered with a 0.22 μm filter head. The obtained filtrate was measured at 551nm by the N, N-diethylphenylenediamine (DPD)/Peroxidase (POD) method, and the result showed that 28.6 mmol.L -1·g-1 was produced by illumination with visible light for 150 min.
1.6, 30Mg of the non-metal doped graphite phase carbon nitride prepared in example 6 was placed in a mixture of 30ml of distilled water and 10ml of isopropanol, and the pH was adjusted to 9 using 1M sodium hydroxide and 1M perchloric acid. The mixed solution is placed under a light source with the wavelength more than 400nm, and oxygen is introduced at the flow rate of 0.2L/min. 2.0ml of the suspension was taken every 30min and the catalyst was filtered with a 0.22 μm filter head. The obtained filtrate was measured at 551nm by the N, N-diethylphenylenediamine (DPD)/Peroxidase (POD) method, and the result showed that 31.3 mmol.L -1·g-1 was produced by illumination with visible light for 150 min.
1.7, 30Mg of the non-metal doped graphite phase carbon nitride prepared in example 7 was placed in a mixture of 30ml of distilled water and 10ml of isopropanol, and the pH was adjusted to 9 using 1M sodium hydroxide and 1M perchloric acid. The mixed solution is placed under a light source with the wavelength more than 400nm, and oxygen is introduced at the flow rate of 0.2L/min. 2.0ml of the suspension was taken every 30min and the catalyst was filtered with a 0.22 μm filter head. The obtained filtrate was measured at 551nm by the N, N-diethylphenylenediamine (DPD)/Peroxidase (POD) method, and the result showed that the irradiation with visible light for 150min resulted in 33.5 mmol.L -1·g-1.
(2) Testing of degradation organics: the catalyst is prepared by adopting nonmetal-doped graphite-phase carbon nitride synthesized in the example 2, filtering hydrogen peroxide filtrate after photocatalytic reaction, taking p-nitrophenol and rhodamine B as target pollutants, taking ultraviolet light as a light source, sampling at intervals of 5-30 min, measuring absorbance at 400nm (4-nitrophenol) and 554nm (rhodamine B) respectively, using a CEL-HXF300-T3 light source system as an instrument, measuring the concentration change of the pollutants through a UV-Vis spectrum, and using a T-UV1900 type ultraviolet visible spectrophotometer as the instrument. The specific detection mode is as follows:
2.1A 30mg sample of photocatalyst was added to 30ml of a solution containing 1ml of isopropanol and the pH was adjusted to 3. The mixed solution was placed under a light source with a wavelength of > 400nm, and after 2.5 hours of reaction, the suspension was filtered with a 0.22 μm filter to obtain a hydrogen peroxide solution. 10ml of the obtained filtrate and 0.15ml of 100 mg/L4-nitrophenol solution were taken, 19.85ml of distilled water was added, and the mixture was irradiated with ultraviolet light (300 nm < lambda < 400 nm) for 120 minutes, sampled every 20 minutes, and absorbance was measured at 400 nm. The result of the used instrument which is a CEL-HXF300-T3 light source system shows that the degradation rate of 4-nitrophenol reaches 94.3% after 120min of illumination.
Fig. 5 shows degradation of 4-nitrophenol by non-metal doped graphite phase carbon nitride under ultraviolet light, wherein "ultraviolet light" in fig. 5 means that the system only contains 4-nitrophenol, no catalyst and hydrogen peroxide are added, and "ultraviolet light+hydrogen peroxide" means that the non-metal doped graphite phase carbon nitride prepared in example 2 adopts the detection mode in 2.1 and adopts hydrogen peroxide as an oxidant, and the pollutant is subjected to oxidative decomposition under the irradiation of ultraviolet light for performance test. The addition of hydrogen peroxide is shown to further increase the degradation rate of 4-nitrophenol.
Fig. 6 is a graph comparing the degradation of 4-nitrophenol by hydrogen peroxide produced from the carbon nitride produced in comparative example 1 (i.e., the carbon nitride of fig. 6) and the non-metal doped carbon nitride produced in example 2 (i.e., the modified carbon nitride of fig. 6), which shows a very significant improvement over the carbon nitride produced in comparative example 1 in the non-metal doped graphite phase produced in example 2 due to the excellent photocatalytic activity of the non-metal doped graphite phase produced in example 2 in a visible light driven two electron oxygen reduction reaction. And more hydrogen peroxide is generated as an oxidant for degrading the 4-nitrophenol, thereby improving the degradation rate of the 4-nitrophenol.
2.2A 30mg sample of the photocatalyst was added to 30ml of an aqueous solution containing 1ml of isopropanol and the pH was adjusted to 3. The mixed solution was placed under a light source at a wavelength of > 400nm, and after 2.5 hours of reaction, the solution was filtered with a 0.22 μm filter head. 5ml of the obtained filtrate and 0.3ml of 100 mg/L4-nitrophenol solution were taken, 24.7ml of distilled water was added, and the mixture was irradiated with ultraviolet light (300 nm < lambda < 400 nm) for 120 minutes, sampled every 20 minutes, and absorbance was measured at 400 nm. The result shows that the degradation rate of 4-nitrophenol reaches 60% after 120min of illumination.
2.3A 30mg sample of the photocatalyst was added to 30ml of an aqueous solution containing 1ml of isopropanol and the pH was adjusted to 4. The mixed solution was placed under a light source at a wavelength of > 400nm, and after 3 hours of reaction, the solution was filtered with a 0.22 μm filter head. 2ml of the obtained filtrate and 0.15ml of 100mg/L rhodamine B solution were taken, 17.85ml of distilled water was added, and the mixture was irradiated with ultraviolet light (300 nm < lambda < 400 nm) for 40 minutes, sampled every 10 minutes, and absorbance was measured at 554 nm. The result shows that the rhodamine B degradation rate reaches 97.2% after 40min of illumination.
(3) The products prepared in example 2, comparative example 1 and comparative example 2 were tested in the same manner as in 1.2, specifically, 30mg of the product was placed in a mixture of 30ml of distilled water and 10ml of isopropyl alcohol, and the pH was adjusted to 3 using 1M sodium hydroxide and 1M perchloric acid. The mixed solution is placed under a light source with the wavelength more than 400nm, and oxygen is introduced at the flow rate of 0.2L/min. 1.5ml of the suspension was taken every 30min and filtered with a 0.22 μm filter head. The obtained filtrate was measured for absorbance at 551nm by N, N-diethylphenylenediamine (DPD)/Peroxidase (POD) method, and the amount of hydrogen peroxide produced was shown in Table 1
TABLE 1 Hydrogen peroxide production from different carbon nitride materials
Example 2 and comparative example 2 were prepared by two different methods, respectively, and in example 2, carbon nitride was prepared first, and then, carbon nitride was mixed with sodium tetraborate and then calcined, and in comparative example 2, melamine and sodium tetraborate were directly mixed and then calcined.
As can be seen from Table 1, in comparison with comparative example 1, the concentration of hydrogen peroxide generated after the non-metal doped graphite phase carbon nitride prepared by the preparation method of calcination is mixed for half an hour in comparative example 2 is not increased, but rather is reduced, because the presence of the boron-containing compound affects the polymerization of carbon nitride during calcination, and the two-stage calcination method of the present invention not only avoids the problem, but also is beneficial to further improving the catalytic performance.
When the nonmetallic doped graphite phase carbon nitride is prepared, firstly, a nitrogen-containing organic matter is adopted to prepare the carbon nitride, then, a nonmetallic element is doped to form an association compound with nitrogen vacancy, so that a strong exciton effect can be weakened, and self-dissociation of bound excitons into free carriers is promoted under the environmental condition. For example, for the escherichia coli (ESCHERICHIA COIL), the hydrogen peroxide generated by the nonmetallic doped graphite-phase carbon nitride prepared by the method has excellent killing performance for the escherichia coli, and the hydrogen peroxide generated by the nonmetallic doped graphite-phase carbon nitride prepared by the method can be further used for practical life.
In the prior art, as disclosed in chinese patent application CN113426470a, a co-doped carbon nitride of potassium, chlorine and iodine, a preparation method thereof and a method for preparing hydrogen peroxide by photocatalysis are disclosed, wherein the charge transfer resistance of the carbon nitride still cannot be reduced due to non-metal doping, and excessive defects may cause formation of new charge recombination centers, but adverse to photocatalysis reaction, and a co-doped carbon nitride material of specific three elements K, cl and I is adopted, which is used as a photocatalyst to produce hydrogen peroxide by photocatalysis under the drive of visible light at a rate as high as 13.1mmol·g -1·h-1.
The invention only adopts single nonmetallic doped carbon nitride, takes boron as an example, and introduces boron-nitrogen vacancy association after boron doping, so that the strong exciton effect can be weakened, and the self-dissociation of bound exciton into free carriers is promoted under the environmental condition, so that the prepared nonmetallic doped graphite-phase carbon nitride has good photocatalytic performance, and the hydrogen peroxide production rate of the nonmetallic doped graphite-phase carbon nitride prepared by the invention is up to 23.3 mmol.L -1·g-1·h-1 under the visible light irradiation of 60 min. Compared with the prior art, 77.86 percent of the preparation method is improved, and the nonmetal-doped graphite phase carbon nitride prepared by the preparation method has high-efficiency visible light catalytic activity.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. The preparation method of the nonmetallic doped graphite phase carbon nitride is characterized by comprising the following steps of:
Calcining the nitrogen-containing organic matter at 500-600 ℃ in the atmosphere of protective gas to obtain a catalyst;
Mixing a catalyst with a nonmetallic compound to obtain a mixture;
calcining the mixture at 360-450 ℃ in the atmosphere of protective gas to obtain the nonmetallic doped graphite phase carbon nitride.
2. The method for preparing nonmetallic doped graphite-phase carbon nitride according to claim 1, wherein the nitrogen-containing organic matter is one or more of cyanamide, dicyandiamide and melamine.
3. The method for preparing nonmetallic doped graphite-phase carbon nitride according to claim 1, wherein the calcination time of the nitrogen-containing organic matter is 4-6 hours, and the heating rate is 2.5-5 ℃/min.
4. The method for preparing non-metal doped graphite phase carbon nitride according to claim 1, wherein the non-metal in the non-metal compound is one or more of boron, sulfur, nitrogen and phosphorus.
5. The method for preparing nonmetallic doped graphite-phase carbon nitride according to claim 1, wherein the mixing is grinding mixing, and the grinding time is 0.5-3h.
6. The method for preparing non-metal doped graphite phase carbon nitride according to claim 1, wherein the mass ratio of the catalyst to the non-metal compound is 1:2-10.
7. The method for preparing non-metal doped graphite phase carbon nitride according to claim 1, wherein the calcination time of the mixture is 2-5 hours, and the heating rate is 2.5-5 ℃/min.
8. A non-metal doped graphite phase carbon nitride prepared by the method of any one of claims 1-7.
9. Use of the non-metal doped graphite phase carbon nitride of claim 8 in the photocatalytic preparation of hydrogen peroxide.
10. The application of the non-metal doped graphite phase carbon nitride in preparing hydrogen peroxide by photocatalysis according to claim 9, which is characterized in that the hydrogen peroxide is prepared by taking visible light as a light source, taking alcohol substances as sacrificial agents, adding the non-metal doped graphite phase carbon nitride, adjusting the pH to 1-9 and introducing oxygen.
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