CN110694660B - Heterogeneous element doped carbon nitride photocatalytic material and preparation method and application thereof - Google Patents
Heterogeneous element doped carbon nitride photocatalytic material and preparation method and application thereof Download PDFInfo
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- 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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Abstract
The invention discloses a heterogeneous element doped carbon nitride photocatalytic material and a preparation method and application thereof. The preparation method of the heterogeneous element doped carbon nitride photocatalytic material comprises the following steps: (1) reacting a graphite-phase carbon nitride precursor with a plant extract in a solution to obtain a hydrogel material, wherein the plant extract is a mixture which is obtained by extracting plants as raw materials and contains a phosphorus-containing compound and inositol; freezing and drying the hydrogel material to obtain an aerogel material; (2) and roasting the aerogel material by temperature programming under the protection of inert gas to prepare the heterogeneous element doped carbon nitride photocatalytic material. The invention utilizes the electrostatic and hydrogen bond action between the plant extract and the graphite phase carbon nitride precursor to orderly arrange and assemble the materials, thereby improving the photocatalysis performance, and the used phosphorus source has no toxic hazard and side effect, and the product has high purity, simple process flow and high hydrogen production rate, and is suitable for industrialized large-scale production.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a heterogeneous element doped carbon nitride photocatalytic material and a preparation method and application thereof.
Background
In the graphite phase carbon nitride (g-C)3N4) In the catalyst, g-C with a stable layered structure similar to graphene3N4The method is widely applied to the field of heterogeneous catalysis, the forbidden band width and the semiconductor band edge position of the method can meet the thermodynamic requirement of photocatalytic conversion, and compared with other photocatalysts, the method has the advantages that: good thermal stability and chemical stability, rich sources and simple preparation process. g-C3N4The structure of (2) determines that it has wide application. At present, g-C3N4Mainly applied to hydrogen production by photolysis of water and CO photocatalytic reduction2The application of the material is limited to a certain extent, so that the modification of the carbon nitride material also becomes a hot spot, wherein the effect of modifying the non-metal doping is better, for example, g-C by a phosphorus source3N4Modification due to phosphorus sources and formation of g-C3N4The precursors are not only simply mixed, but also are tightly crosslinked together due to the action of acid and alkali, but phosphide used in the phosphorus doping process has toxic and harmful effects on human bodies. In the pair of phosphorus sources g-C3N4Modification studies, for example, Ran et al [ Ran M, Li J, Wen C, et al, efficient and stable photocatalytic NO removaval on C self-timed g-C3N4:electronic structure and reaction mechanism[J].Catalysis Science and Technology,2018:10.1039]Synthesis of porous P-g-C with Melamine and AEP (2-aminoethyl phosphoric acid)3N4Research results show that the acid-base action and van der Waals force between melamine and AEP promote the generation of uniform mesoporous structure, so that P-g-C3N4Has larger specific surface area, and is beneficial to increasing the catalytic capability.
Ma et al [ Ma X, Lv Y, Xu J, et al3N4 via Doping of Nonmetal Elements:AFirst-Principles Study[J].Journal of Physical Chemistry C,2012,116(44):23485-23493]Synthesizing P-g-C with flower-shaped structure by using carbon fiber paper, melamine and ethylene diphosphate as precursors3N4. Researches find that acid-base action among carbon fiber paper, melamine and ethylene diphosphonic acid promotes the precursor to be adsorbed on the carbon fiber paper, thereby being beneficial to P-g-C3N4Growth of flower-like nanostructures and P-g-C3N4Coupling with carbon fiber paper. Overall, the phosphorus source and the formation of g-C3N4The acid-base action between the precursors promotes the introduction of impurity elements into the structure, and is beneficial to the generation of other homogeneous structures similar to mesopores and controllable appearances, thereby enhancing the P-g-C under the multi-acting force of doping and appearance3N4The catalytic ability of (a).
CN109395764A discloses a preparation method of phosphorus-doped carbon nitride, a product and an application thereof, wherein phosphorus-doped carbon nitride is prepared by a preparation method of firstly carrying out reaction to obtain atom-level doped precursors of different elements and then carrying out roasting. The method adopts melamine as a carbon nitride precursor, firstly, melamine and polyphosphoric acid are subjected to chemical reaction to promote phosphorus atoms and the melamine to form atomic-level mixing, then, the melamine polyphosphate synthesized by the reaction is roasted to prepare the uniformly doped phosphorus-doped carbon nitride, and the phosphorus-doped carbon nitride prepared by the method is uniformly doped with phosphorus, but the photocatalytic performance of the carbon nitride needs to be further improved.
For another example, CN107008496A discloses a method for preparing oleophilic modified graphite-phase carbon nitride, which comprises mixing graphite-phase carbon nitride with an organic modifier, adding glacial acetic acid for ultrasonic treatment, transferring to a hydrothermal kettle for hydrothermal reaction, washing the sample to neutrality, and drying to obtain modified graphite-phase carbon nitride.
Disclosure of Invention
In order to solve at least part of technical problems in the prior art, the invention provides an improved preparation method of a heterogeneous element doped carbon nitride photocatalytic material. The present invention has been accomplished based on this. Specifically, the present invention includes the following.
In a first aspect of the present invention, a method for preparing a heterogeneous element doped carbon nitride photocatalytic material is provided, which comprises the following steps:
(1) reacting a graphite-phase carbon nitride precursor with a plant extract in a solution to obtain a hydrogel material, wherein the plant extract is a mixture which is obtained by extracting a plant as a raw material and contains a phosphorus-containing compound and inositol;
(2) and roasting the aerogel material by temperature programming under the protection of inert gas to prepare the heterogeneous element doped carbon nitride photocatalytic material.
In certain embodiments, the graphite phase carbon nitride precursor includes melamine, dicyandiamide, and the like, in accordance with the method of the present invention for preparing a heterogeneous element doped carbon nitride photocatalytic material.
In some embodiments, according to the method for preparing a heterogeneous element doped carbon nitride photocatalytic material of the present invention, the extraction of the plant extract comprises the steps of:
a. soaking at least one plant material selected from the group consisting of rice hulls, distiller's grains, rice bran and rapeseed meal in an acid solution to obtain a soaking solution;
b. filtering the obtained soak solution, and then neutralizing the filtrate with an alkaline solution to obtain a neutralized solution;
c. filtering the neutralized solution to obtain a precipitate, and acidifying the obtained precipitate to obtain a plant extract.
In certain embodiments, according to the method for preparing a heterogeneous element doped carbon nitride photocatalytic material of the present invention, the pH of the acid solution is 2.0 to 3.0.
In certain embodiments, according to the method for preparing a heterogeneous element-doped carbon nitride photocatalytic material of the present invention, at least one selected from the group consisting of urea, sodium sulfate, ammonium carbonate, ammonium sulfate, and sodium chloride is added to the soak solution.
In some embodiments, according to the preparation method of the heterogeneous element doped carbon nitride photocatalytic material of the present invention, the temperature rise rate of the temperature programming is 2-10 ℃/min, and the temperature is kept for 2-5 hours after the temperature is raised to 500-600 ℃.
In certain embodiments, the method for preparing a heterogeneous element doped carbon nitride photocatalytic material according to the present invention further comprises a step of freeze-drying the gel material between steps (1) and (2).
In certain embodiments, a method of preparing a heterogeneous element doped carbon nitride photocatalytic material according to the present invention comprises the steps of:
adding melamine into water, uniformly stirring to obtain a mixture, adding the plant extract into the mixture, and continuously stirring until hydrogel is obtained; freezing and drying the hydrogel to prepare an aerogel precursor; and then, putting the precursor into a tube furnace, heating to 600 ℃ in an argon atmosphere, and keeping for 3h at the heating rate of 2-8 ℃/min to obtain the phosphorus-doped carbon nitride photocatalytic material.
In a second aspect of the invention, a heterogeneous element doped carbon nitride photocatalytic material is provided, which is prepared by the preparation method of the invention.
In a third aspect of the present invention, there is provided an application of the heterogeneous element doped carbon nitride material of the second aspect in hydrogen production by photocatalytic decomposition of water.
In the preparation of the precursor, the plant extract and the graphite-phase carbon nitride precursor form self-assembled hydrogel through electrostatic interaction and hydrogen bond interaction, and the hydrogel is freeze-dried to obtain a fluffy aerogel precursor, so that the fluffy aerogel precursor is favorable for orderly arranging and assembling the material in a high-temperature roasting process, and the performance of the catalyst is improved. In addition, the invention finds that the plant extract not only provides a phosphorus source for the preparation process, but also optimizes the structure of the catalyst and improves the porosity. The heterogeneous element doped carbon nitride photocatalytic material has high purity, the used phosphorus source has no toxic or side effect, no by-product is mixed, the process flow is simple, the hydrogen production rate is high, and the method is suitable for industrial large-scale production.
Drawings
FIG. 1 is a schematic diagram of an exemplary process for preparing a heterogeneous element doped carbon nitride photocatalytic material.
Fig. 2 is an X-ray diffraction pattern of an exemplary heterogeneous element doped carbon nitride photocatalytic material.
Fig. 3 is a Scanning Electron Microscope (SEM) image of an exemplary heterogeneous element doped carbon nitride photocatalytic material.
FIG. 4 is a graph of photocatalytic water splitting to hydrogen production performance of an exemplary heterogeneous element doped carbon nitride photocatalytic material.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that the upper and lower limits of the range, and each intervening value therebetween, is specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
In a first aspect of the present invention, a method for preparing a heterogeneous element doped carbon nitride photocatalytic material is provided, which comprises the following steps:
(1) reacting a graphite-phase carbon nitride precursor with a plant extract in a solution to obtain a gel material, wherein the plant extract is a mixture which is obtained by extracting a plant as a raw material and contains a phosphorus-containing compound and inositol;
(2) and roasting the gel material by temperature programming under the protection of inert gas to prepare the heterogeneous element doped carbon nitride photocatalytic material.
Step (1)
Specifically, the graphite phase carbon nitride precursor in step (1) of the present invention is generally a C-rich and N-rich compound, examples of which include, but are not limited to, melamine, dicyandiamide, cyanamide, thiourea and urea. The plant extract of the invention is a mixture obtained by extracting plants as raw materials, and comprises a phosphorus-containing compound and inositol. In the invention, the phosphorus-containing compound can provide heterogeneous element phosphorus for the graphite-phase carbon nitride. The invention finds that, unlike the prior art which uses pure artificially synthesized compounds, natural products extracted from plants can be directly used as a source of heterogeneous elements, and the obtained catalyst has excellent effect and no toxic or side effect.In addition, the plant extract of the present invention further comprises inositol. The present invention has surprisingly found that the presence of inositol can optimise the structure of the catalyst and increase the porosity. The reason may be that inositol is used as pore forming agent during the condensation polymerization of structural units in the heterogeneous element doping process, the structural units and the pore forming structure morphology are optimized, the synthesized material has larger specific surface area, and g-C is formed based on the doping of heterogeneous elements3N4The optimization of lattice defects and the change of morphology can improve the light absorption capacity of the material and provide more active sites, and finally improve the photocatalytic performance of the material. In certain embodiments, the phosphorus-containing compound and inositol may be present as the same material, e.g., phytic acid. In certain embodiments, the phosphorus-containing compound is present with inositol as two different species, e.g., an organophosphorus compound and a minor amount of inositol.
The plant extract can be obtained by extracting various plants as raw materials. Specifically, as the plant as the raw material of the present invention, a plant rich in a desired hetero atom (e.g., P, S, etc.) is preferable, including the whole plant, and also including a partial material of the plant, such as a seed part, or a processing by-product of the plant, etc. In certain embodiments, examples of the plant include, but are not limited to, rice hulls, distillers grains, rice bran, and rapeseed meal. One or more of the above-mentioned substances may be used in the present invention.
In an exemplary embodiment, the plant extract of the present invention is extracted by precipitation. Specifically, a plant such as rapeseed meal is subjected to pickling solution treatment, the filtered soaking solution is neutralized with an alkali solution to obtain a neutralized solution, the neutralized solution is filtered to obtain a precipitate, and the obtained precipitate is subjected to secondary acidification to obtain a plant extract. Wherein the pH value of the pickle liquor is 2.0-3.0, thereby preventing the phosphorus-containing compound from being combined with protein such as globulin, generating excessive compound which is insoluble in acid and influencing the extraction quality, and ensuring the extraction rate of the phosphorus-containing compound.
In a preferred embodiment, at least one selected from the group consisting of urea, sodium sulfate, ammonium carbonate, ammonium sulfate and sodium chloride is added to the soaking solution at the time of the precipitation method. Preferably, sodium sulfate is chosen as an aid to prevent the introduction of proteins from affecting the building blocks. In addition, in the precipitation method, sodium sulfate is precipitated by the precipitation salt, and sulfur element can be provided in the process of doping the heterogeneous elements.
The extract of the present invention can be used for detection of phosphorus-containing compounds and inositol by known detection means. For example, the phosphorus-containing compound and its content are detected by titration, high-pressure liquid chromatography, spectrophotometry, or the like. In a specific embodiment, sulfosalicylic acid is used and placed in a spectrophotometer to detect under the condition of pH 6-7, the wavelength is set to be 500-510nm, and preferably, the wavelength is set to be 505 nm. In addition, the presence and amount of inositol can be detected by known methods. For example, inositol can be detected using the national standard GB/T5009.196-2003.
In a preferred embodiment, the present invention further comprises the step of freeze-drying the hydrogel material after formation thereof, followed by the step (2) below, wherein the freeze-drying is carried out by a conventional procedure. According to the invention, a fluffy aerogel precursor can be obtained through freeze drying, so that the catalytic performance is further improved.
Step (2)
The step (2) is a step of obtaining the heterogeneous element doped carbon nitride photocatalytic material. Namely, the aerogel material is roasted by temperature programming under the protection of inert gas, and the heterogeneous element doped carbon nitride photocatalytic material is prepared. Preferably, the temperature rising rate of the temperature programming of the invention is 2-10 ℃/min, and the temperature is kept for a certain time after reaching the required temperature. For example, after heating to 500-600 ℃ for 2-5 hours. More preferably, the temperature rise rate is 2-8 ℃/min, and the temperature is kept for 2-5 hours after rising to 520-600 ℃. The inert gas of the present invention may be selected from one of the group consisting of helium, nitrogen and argon, preferably argon. During this process, the structure of the precursor, e.g. melamine, rearranges to form triazine structural units, which further condense to form carbon nitride material when the temperature reaches the maximum temperature of the programmed temperature. The phosphorus-containing compound and inositol in the plant extract in the step (1) replace carbon and nitrogen elements in a triazine structural unit in the step and form a pore-forming knotTo form g-C3N4The method has the advantages that the lattice defect is overcome, the effect of efficient separation of photo-generated electron-hole pairs is achieved, the photocatalytic performance is improved, in the preparation process of the self-assembled melamine precursor, the plant extract and melamine form self-assembled hydrogel through electrostatic interaction and hydrogen bond interaction, the hydrogel is subjected to freeze drying to obtain a fluffy aerogel precursor, the plant extract is a phosphorus source, the precursor is subjected to pyrolysis and polymerization in the roasting process to obtain the phosphorus-doped carbon nitride photocatalytic material, and the fluffy precursor is favorable for orderly arrangement and assembly of the material in the high-temperature roasting process, so that the performance of the catalyst is improved.
Example 1
This example is an exemplary extraction and detection process of plant extracts used in the preparation of heterogeneous element doped carbon nitride photocatalytic materials. The method comprises the following specific steps:
a. soaking the rapeseed meal in sodium sulfate and acetic acid solution to obtain soaking solution, and adjusting the pH value of the solution to 2.5 by using a pH meter;
b. filtering the obtained soaking solution, neutralizing with 10% sodium hydroxide solution to obtain neutralized solution, and adjusting pH value of the solution to 7.5 by using a pH meter;
c. filtering the neutralized solution to obtain precipitate, performing secondary acidification of the precipitate with 1mol/l hydrochloric acid, and adjusting pH of the solution to 1.5 with pH meter to obtain plant extract.
Example 2
This example is another exemplary extraction and detection process of plant extracts used in the preparation of heterogeneous element doped carbon nitride photocatalytic materials. The method comprises the following specific steps:
a. soaking the rapeseed meal in sodium sulfate and acetic acid solution to obtain soaking solution, and adjusting the pH value of the solution to 2.5 by using a pH meter;
b. filtering the obtained soaking solution, neutralizing with a solution containing 10% of sodium hydroxide and 5% of ammonium sulfate to obtain a neutralized solution, and adjusting the pH value of the solution to 7.5 by using a pH meter;
c. filtering the neutralized solution to obtain precipitate, performing secondary acidification of the precipitate with 1mol/l hydrochloric acid, and adjusting pH of the solution to 1.5 with pH meter to obtain plant extract.
Example 3
FIG. 1 is a schematic diagram of an exemplary process for preparing a heterogeneous element doped carbon nitride photocatalytic material. As shown in FIG. 1, the melamine and plant extract can be complexed to form hydrogel, and the P-C is finally obtained3N4The photocatalyst material is brown, which is beneficial to the absorption and utilization of light, thereby improving the photocatalytic performance.
The preparation method comprises the following specific steps: 20mmol of melamine were first weighed into 10ml of water and after stirring well, 200. mu.L of the plant extract (50%, example 1) were added to the mixture and stirring was continued until a hydrogel was obtained. And freezing and drying the prepared hydrogel to obtain an aerogel precursor. And then, putting the self-assembly aerogel precursor prepared in the step into a tubular furnace, heating to 600 ℃ in an argon atmosphere, and keeping for 3h at the heating rate of 2 ℃/min to obtain the heterogeneous carbon nitride-doped photocatalytic material.
Example 4
This example is another exemplary fabrication process of a heterogeneous element doped carbon nitride photocatalytic material. The preparation process comprises the following steps: 30mmol of melamine were first weighed into 10ml of water and after stirring well, 200. mu.L of the plant extract (50%, example 1) were added to the mixture and stirring was continued until a hydrogel was obtained. And freezing and drying the prepared hydrogel to obtain an aerogel precursor. And then, putting the self-assembly aerogel precursor prepared in the step into a tubular furnace, heating to 550 ℃ in an argon atmosphere, and keeping for 3h at the heating rate of 2 ℃/min to obtain the heterogeneous carbon nitride-doped photocatalytic material.
Example 5
This example is another exemplary fabrication process of a heterogeneous element doped carbon nitride photocatalytic material. The preparation process comprises the following steps: 40mmol of melamine were first weighed into 10ml of water and after stirring well, 200. mu.L of the plant extract (50%, example 2) were added to the mixture and stirring was continued until a hydrogel was obtained. And freezing and drying the prepared hydrogel to obtain an aerogel precursor. And then, putting the self-assembly aerogel precursor prepared in the step into a tubular furnace, heating to 500 ℃ in an argon atmosphere, and keeping for 3h at the heating rate of 2 ℃/min to obtain the heterogeneous carbon nitride-doped photocatalytic material.
Test example
Measuring phosphorus-containing compounds in the extractive solution by spectrophotometry, mixing 1ml of plant extract and 1ml of trichloroacetic acid with concentration of 15%, placing in ice box for 2h, centrifuging, collecting supernatant, diluting to 15ml with distilled water under pH 6.5, adding 0.5ml of sulfosalicylic acid with concentration of 0.3% and ferric chloride with concentration of 0.03% into 1.5ml of diluent, mixing thoroughly, placing in spectrophotometer, detecting with wavelength of 505nm, and calculating with the following formula:
wherein: c is the concentration of the phosphorus-containing compound (mg/mL); a is absorbance.
FIG. 2 is an X-ray diffraction pattern of the heteroelement-doped carbon nitride photocatalytic material of example 3. As can be seen in the figure, the phase of the precursor formed by the complexation of melamine and the plant extract is still melamine, and the comparison shows that P-C3N4And g-C3N4The XRD spectrogram of the material is not changed after the phosphorus element is doped, which indicates that the phase is not changed by the doping of the phosphorus element.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the heterogeneous element doped carbon nitride photocatalytic material of example 3, which shows that C, O, P elements are uniformly distributed in the catalytic material, and the g-C obtained is illustrated3N4Is doped with P element.
In order to verify the photocatalytic activity of the material of the present invention, the performance of hydrogen production by photocatalytic decomposition was measured using the heterogeneous element-doped carbon nitride material prepared in example 3. The method comprises the following specific steps:
50mg of carbon nitride material was dispersed in an aqueous solution containing 10% by volume of methanol, and then a solution containing 3 wt.% equivalent of chloroplatinic acid was added to the solutionContinuously introducing argon gas into the solution to remove oxygen in the water solution, continuously irradiating the solution by using a 300W xenon lamp light source, measuring the hydrogen production by adopting a gas chromatography, wherein the result of catalytically decomposing the water to produce hydrogen is shown in figure 4, as shown in figure 4, the performance of the obtained heterogeneous element doped carbon nitride material for photocatalytic decomposition of water to produce hydrogen is greatly improved, and the hydrogen is common g-C3N4About 4 times as much catalytic material.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Many modifications and variations may be made to the exemplary embodiments of the present description without departing from the scope or spirit of the present invention. The scope of the claims is to be accorded the broadest interpretation so as to encompass all modifications and equivalent structures and functions.
Claims (8)
1. A preparation method of a heterogeneous element doped carbon nitride photocatalytic material is characterized by comprising the following steps:
reacting a graphite-phase carbon nitride precursor with a plant extract in a solution to obtain a hydrogel material, wherein the plant extract is a mixture which is obtained by extracting a plant as a raw material and contains a phosphorus-containing compound and inositol, and the extraction step comprises the following steps: soaking at least one plant material selected from the group consisting of rice hulls, distiller's grains, rice bran and rapeseed meal in an acid solution to obtain a soaking solution; filtering the obtained soak solution, and then neutralizing the filtrate with an alkaline solution to obtain a neutralized solution; filtering the neutralized solution to obtain a precipitate, and acidifying the precipitate to obtain a plant extract;
obtaining an aerogel material by freeze-drying the hydrogel material;
and roasting the aerogel material by temperature programming under the protection of inert gas to prepare the heterogeneous element doped carbon nitride photocatalytic material.
2. The method of claim 1, wherein the graphite-phase carbon nitride precursor is at least one selected from the group consisting of melamine, dicyandiamide, cyanamide, thiourea and urea.
3. The method for preparing a heterogeneous element doped carbon nitride photocatalytic material according to claim 1, wherein the pH of the acid solution is 2.0-3.0.
4. The method of claim 1, wherein at least one selected from the group consisting of urea, sodium sulfate, ammonium carbonate, ammonium sulfate and sodium chloride is added to the soaking solution.
5. The method as claimed in claim 1, wherein the temperature-raising rate of the programmed temperature-raising is 2-10 ℃/min, and the temperature-raising is maintained for 2-5 hours after the temperature-raising is up to 500-600 ℃.
6. The method for preparing the heterogeneous element doped carbon nitride photocatalytic material according to claim 5, is characterized by comprising the following steps:
adding melamine into water, uniformly stirring to obtain a mixture, adding the plant extract into the mixture, and continuously stirring until hydrogel is obtained; freezing and drying the hydrogel to prepare an aerogel precursor; and then, putting the precursor into a tube furnace, heating to 500-600 ℃ in an inert gas atmosphere, and keeping for 2-5h, wherein the heating rate is 2-10 ℃/min, so as to obtain the carbon nitride photocatalytic material doped with the heterogeneous elements.
7. A heterogeneous element doped carbon nitride photocatalytic material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 6.
8. Use of a heterogeneous element doped carbon nitride photocatalytic material in reforming hydrogen production, characterized in that the heterogeneous element doped carbon nitride photocatalytic material is according to claim 7.
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