TWI688428B - A graphitic carbon nitride- heterogeneous element doped graphene photocatalyst and manufacturing method thereof - Google Patents

Abstract

The present disclosure provides a graphitic carbon nitride- heterogeneous element doped graphene photocatalyst comprising a graphene doped with a heterogeneous element and a graphitic carbon nitride. A chemical bond is formed between the heterogeneous element of the graphene and the graphitic carbon nitride. The present disclosure also provides a method of manufacturing thereof.

Description

Graphite phase carbon nitride-doped heteroelement graphene photocatalyst and manufacturing method thereof

The present disclosure relates to a photocatalyst, in particular to a graphite phase carbon nitride-doped heterogeneous element graphene photocatalyst and a manufacturing method thereof.

Photocatalysis is the semiconductor material 料 divided into photogenerated electrons and electricity 飯 under a certain wavelength of light, and then the photogenerated electrons and electricity 洞 are combined with the reactants to form an oxidative or reductive reaction. During the reaction process, this semiconductor material 料That is, the photocatalyst itself has changed. As an efficient, safe and environmentally friendly technology, photocatalysis technology has received widespread attention at present, and has broad application prospects in the fields of photolysis of water to produce hydrogen and pollutants.

Graphite phase carbon nitride (gC ₃ N ₄ ) is a new type of photocatalyst that is not 金, and is composed of only C and N, and its price is 便suitable. The energy gap is about 2.7 eV. Under the sunlight, due to the transition of electrons in the valence band, an electron-electricity pair is formed, which can further generate active carriers, catalyze the hydrolysis of hydrogen to produce oxygen. However, due to the rapid recombination of electronic electricity and the small specific surface area, the photocatalytic performance of gC ₃ N ₄ has not reached 理.

There are currently three main methods of improvement: physical modification, chemical modification, and microstructure adjustment, but the effects of the current modification methods are relatively simple and limited. Therefore, it is important to provide a catalyst that can improve the utilization of sunlight and improve the photocatalytic activity.

According to an embodiment of the present disclosure, the present disclosure provides a graphite phase carbon nitride-doped heteroelement graphene photocatalyst. The catalyst includes graphene doped with heterogeneous elements and graphite phase carbon nitride, wherein the graphene doped heterogeneous element and the graphite phase carbon nitride have a chemical bond.

According to another embodiment of the present disclosure, the present disclosure further provides a method for manufacturing a graphite phase carbon nitride-doped heteroelement graphene photocatalyst. The manufacturing method includes providing a carrier gas into the reaction tank; providing a carbon nitride precursor upstream of the carrier gas flow path; providing a doped graphene layer downstream of the carrier gas flow path; and heating gasification nitridation The carbon precursor is a gas-phase carbon nitride precursor, which moves the gas-phase carbon nitride precursor from the upstream of the carrier gas flow path to the downstream, and deposits the gas-phase carbon nitride precursor on the doped graphene layer. To form a catalyst.

The present disclosure provides a graphite phase carbon nitride-doped heteroelement graphene photocatalyst and a manufacturing method of the photocatalyst. The present disclosure uses chemical vapor deposition to deposit a thin layer of graphite-phase carbon nitride on graphene doped with heterogeneous elements, and uses the doping elements of the graphene layer to form a chemical bond with the graphite-phase carbon nitride, and then changes Its electron distribution and regulate the band gap. In addition, the thinning of carbon nitride can increase the specific surface area and increase the effective active position. Uniform composite graphene can improve the transmission of electron holes and reduce the electron hole recombination rate. Doping modification can increase the number of active positions. To improve the catalyst activity and light utilization rate through energy gap adjustment, active position, and reduction of recombination rate.

An embodiment of the present disclosure provides a graphite phase carbon nitride-doped hetero-element graphene photocatalyst. The photocatalyst includes graphene doped with heterogeneous elements; and graphite phase carbon nitride, wherein the doped elements of the graphene layer and the graphite phase carbon nitride have chemical bonds. In one embodiment, the chemical bonding between the doping element of the graphene layer and the graphite phase carbon nitride is sp ³ bonding.

In some embodiments, the doping elements in the doped heterogeneous graphene include nitrogen, boron, phosphorus, sulfur, chlorine, or bromine. In some embodiments, the ratio of the doping heteroelement to the graphene is 1-20 atomic%, such as 0.1-15 atomic%, 1-15 atomic%, and 3-10 atomic%. If the ratio of doping elements is too low, there are few reactive sites, and the modification effect is not obvious; if the ratio of doping elements is too high, it may increase the defects of the material structure, resulting in decreased reactivity.

In some embodiments, the graphite phase carbon nitride has a thin layer structure with a thickness ranging from 0.3 to 4 nm, and the number of layers of the thin film structure is 1-12 layers, such as 1-8 layers. If there are too many layers, the electrons The transmission effect is poor and the reactivity is low.

In some embodiments, the ratio of the doped heteroelement graphene layer to the graphite phase carbon nitride layer is 1-40wt%, for example, 1-30wt%, 5-25wt%, 10-20wt%, if doped heteroelement If the ratio of the graphene layer is too high, the reaction potential is lower than the water reduction potential, and hydrogen production cannot occur; if the ratio is too low, the modification effect is not obvious. In some embodiments, the energy gap between the graphite phase carbon nitride layer and the heterogeneous element-doped graphene layer is 1.6-2.8 eV, such as 2.0-2.8, 2.2-2.6 eV.

In the present disclosure, a graphene oxide aqueous solution is prepared by Hummer redox method and dried to obtain graphene oxide powder, and then doped with heterogeneous elements in graphene, and then deposited on the graphene doped with heterogeneous elements by chemical vapor deposition The thin layer graphite phase carbon nitride layer finally obtains the thin layer graphite phase carbon nitride-doped heteroelement graphene photocatalyst.

Another embodiment of the present disclosure provides a method for manufacturing a graphite phase carbon nitride-doped hetero-element graphene photocatalyst. The manufacturing method includes: providing a carrier gas into a reaction tank, providing a carbon nitride precursor upstream of the carrier gas flow path, and providing a doped graphene layer downstream of the carrier gas flow path, And heating and vaporizing the carbon nitride precursor into a gas phase, so that the carbon nitride precursor moves from the upstream of the carrier gas flow path to the downstream, and the gas-phase carbon nitride precursor is deposited on the doped graphene A thin layer of graphite phase carbon nitride-doped heterogeneous element graphene photocatalyst is formed on the layer.

In one embodiment, the heterogeneous element is nitrogen, boron, phosphorus, sulfur, chlorine, or bromine. In some embodiments, the source of heterogeneous elements is 尿 element, 硫 urea, ammonia gas, boric acid, ammonium borate, 硫 acid, hydrogen hydride, phosphoric acid, ammonium chloride, ammonium fluoride, ammonium bromide or derivatives thereof.

In some embodiments, the ratio of heterogeneous elements to graphene is 1-20 atomic%, such as 0.1-15 atomic%, 1-15 atomic%, and 3-10 atomic%. If the proportion of doped heterogeneous elements is too low, there are fewer reactive sites and the modification effect is not obvious; if the proportion of doped heterogeneous elements is too high, material defects may increase, resulting in decreased reactivity.

In some embodiments, the ratio of the heterogeneous element graphene to the graphite carbon nitride is 1-40 wt%, for example, 1-30 wt%, 5-25 wt%, 10-20 wt%. If the ratio is too high, the reaction potential is lower than the water reduction potential, and hydrogen production cannot occur; if the ratio is too low, the modification effect is not obvious.

In some embodiments, the mass ratio of the doped heteroelement graphene to the carbon nitride precursor is 0.001-0.1 wt%. In some embodiments, the carbon nitride precursor comprises melamine, melamine, monocyanamide, urea, thiourea, ammonia gas, polyethylene polyamine, or derivatives thereof. The carbon nitride precursor may be a solid, liquid, or gas. In some embodiments, the carbon nitride precursor is urea.

In some embodiments, the carrier gas includes nitrogen, argon, ammonia, hydrogen sulfide, or a combination of the foregoing. In some embodiments, the carrier gas is argon. In some embodiments, the carrier gas flow rate is 1-100 ml/min, for example 30-50 ml/min.

In some embodiments, the upstream gasification reaction temperature is between 350 and 900°C, for example, 400-800°C and 500-600°C. In some embodiments, the reaction pressure is between 0 and 50 torr.

In order to make the above-mentioned and other objects, features, and advantages of the present disclosure more obvious and understandable, the embodiments are specifically listed below, and in conjunction with the drawings, detailed descriptions are as follows:

Preparation Example 1: Graphene Oxide

Graphene oxide aqueous solution was prepared by Hummer redox method and dried to obtain graphene oxide powder.

First, 10g flake graphite was added to 10g oxidizer KMnO ₄ and 5g K ₂ FeO ₄ and 0.05g stabilizer boric acid were dispersed in 100mL concentrated sulfuric acid, and after stirring at 5°C for 1.5 hours, additional 5g KMnO ₄ was added at 35°C Stir for 3 hours to complete the oxidation. After that, add 250mL of deionized water at a constant temperature of 95°C, and add 12mL of 30wt% H ₂ O ₂ to the suspension, then centrifuge at 10,000 rpm for 20 minutes to remove the residual graphite, and wash with 1 mol/L HCl, followed by deionized water flow After washing and drying, the product obtains graphene oxide powder.

Example 1: Nitrogen Doped Graphene (NG)

Put 300 mg of graphene oxide powder in a tube furnace and pass argon gas to form a protective atmosphere, and then introduce ammonia gas at a flow rate of 30 ml/min, and increase the temperature to 600-900°C for 2-4 hours. The speed is controlled at 1-10℃/min, so that ammonia gas and graphene oxide powder can fully react. After the natural temperature is lowered, the product is obtained and washed with deionized water. After filtering, it can be dried in a 60-80℃ oven to obtain nitrogen doping. Graphene powder. X-ray photoelectron spectroscopy (XPS) was used to measure the nitrogen and oxygen content, the nitrogen content was about 4-10 atomic%, and the oxygen content was less than 3 atomic%.

Example 2: Thin-layer graphite phase carbon nitride (thin layer gC ₃ N ₄ )

An empty alumina crucible was placed downstream in the tubular furnace, and 10 g of urea was placed in another crucible and placed upstream in the tubular furnace. The pressure in the tube furnace was adjusted to vacuum to 20 torr and argon was introduced at 30 ml/min. The temperature of 600 ℃ in the upstream and 400 ℃ in the downstream was controlled by a three-zone system, and the temperature was naturally lowered after maintaining for 4 hours. After taking the precipitate in the downstream crucible with deionized water and drying it in an oven, a thin layer of gC ₃ N ₄ can be obtained.

Example 3: Thin-layer graphite phase carbon nitride-5wt% nitrogen-doped graphene

Take 40 mg of nitrogen-doped graphene powder in Example 1 and disperse it in an aqueous solution with ultrasonic waves and dry it. Place it in an alumina crucible and place it downstream in the tube furnace. Place 10 g of urea in another crucible and Placed upstream in the tube furnace. The pressure in the tube furnace was adjusted to vacuum to 20 torr and argon was introduced at 30 ml/min. The temperature of 600 ℃ in the upstream and 400 ℃ in the downstream was controlled by a three-zone system, and the temperature was naturally lowered after maintaining for 4 hours. After taking the precipitate in the downstream crucible with deionized water and drying it in an oven, a thin layer of graphite-phase carbon nitride-5wt% nitrogen-doped graphene (gC ₃ N ₄ /5wt% NG) can be obtained.

Embodiment 4: Thin layer graphite phase carbon nitride-10wt% doped graphene

Take 80 mg of nitrogen-doped graphene powder of Example 1 and disperse it in an aqueous solution by ultrasonic wave, dry it, place it in an alumina crucible and place it downstream in the tubular furnace, put 10 g of urea in another crucible and Placed upstream in the tube furnace. The pressure in the tube furnace was adjusted to vacuum to 20 torr and argon was introduced at 30 ml/min. The temperature of 600 ℃ in the upstream and 400 ℃ in the downstream was controlled by a three-zone system, and the temperature was naturally lowered after maintaining for 4 hours. After taking the precipitate in the downstream crucible with deionized water and drying it in an oven, a thin layer of graphite-phase carbon nitride-10wt% nitrogen-doped graphene (gC ₃ N ₄ /10wt% NG) can be obtained.

Example 5: Thin layer graphite phase carbon nitride-20wt% nitrogen-doped graphene

Take 160 mg of the nitrogen-doped graphene powder of Example 1 dispersed in an aqueous solution with ultrasonic waves, dry it in an alumina crucible and place it downstream in the tubular furnace, place 10 g of urea in another crucible and place it Upstream of the tubular furnace. The pressure in the tube furnace was adjusted to vacuum to 20 torr and argon was introduced at 30 ml/min. The temperature of 600 ℃ in the upstream and 400 ℃ in the downstream was controlled by a three-zone system, and the temperature was naturally lowered after maintaining for 4 hours. After taking the precipitate in the downstream crucible with deionized water, drying it in an oven to obtain a thin layer of graphite phase carbon nitride-20wt% nitrogen-doped graphene photocatalyst (gC ₃ N ₄ /20wt% NG).

Comparative Example 1: Solid-phase graphite phase carbon nitride (Bulk gC ₃ N ₄ )

The product in the upstream crucible of Example 2 was washed with deionized water and dried in an oven to obtain graphite carbon nitride.

Comparative Example 2: Physical mixed graphite phase carbon nitride-20wt% nitrogen-doped graphene

After mixing 500mg of graphite phase carbon nitride obtained in Comparative Example 1, 20wt% nitrogen-doped graphene powder was mixed and shaken with a ball mill at a frequency of 25Hz for 1.5 hours, and then filtered, washed, and dried to obtain physical mixed graphite phase carbon nitride -20wt% nitrogen-doped graphene.

Comparative Example 3: Mixed-fired graphite phase carbon nitride-20wt% nitrogen-doped graphene

Disperse 40 mg of nitrogen-doped graphene in an aqueous solution with ultrasound, mix it uniformly with 10 g of urea, a graphite phase carbon nitride precursor, and place it in a crucible. Place the crucible in a tube furnace for calcination: the heating rate is 1-10℃/min, and the temperature is raised to the control temperature of 600℃ and maintained for 4 hours to naturally cool down. After taking the precipitate in the pot and washing with deionized water, drying in an oven can obtain mixed-fired graphite phase carbon nitride-20wt% nitrogen-doped graphene photocatalyst.

Figures 1A and 1B are the results of X-ray diffraction analysis (XRD) analysis of the solid graphite graphite carbon nitride of Comparative Example 1 and the thin graphite graphite carbon nitride of Example 2 respectively. Figure 1A shows that Comparative Example 1 solid-phase polymerized graphite phase carbon nitride has obvious (100) and (002) diffraction peaks at 13.1 ^o and 27.6 ^o, which is consistent with the block 狀g-C3N4 diffraction peak in the standard spectrum; and Figure 1B shows that the vapor deposition product of Example 2 only has a (002) diffraction peak at 27.6 ^o , and a (100) diffraction peak at 13.1 ^o is obvious, which is only (002) with a single layer of gC ₃ N ₄ in the standard spectrum. ) The results of diffraction peaks are similar. In addition, the FWHM of its (002) diffraction peak is wider, showing its smaller size, so it can be seen that the product of vapor deposition is a thin layer of gC ₃ N ₄ .

Fig. 2A is a solid graphite graphite carbon nitride of Comparative Example 1; The TEM photo shows the results. The actual thickness of the stack is about 15nm. Since the single-layer gC ₃ N _{4 is} about 0.33nm, the structure is estimated to be about 45 layers; and FIG. 2B is the thin layer of chemical vapor deposition in Example 2 TEM photo of gC ₃ N ₄ , it is judged from its lattice fringe that the layer 狀 stack layer 數 is about 8-10 layers. The actual measurement of the stack thickness is about 2.5nm, 若 judged by the gC ₃ N ₄ single layer about 0.33nm, and its structure is about 7-8 layers. From the above results, it can be seen that the vapor deposited gC ₃ N ₄ has the characteristics of a thin layer .

The band gap changes before and after recombination of gC ₃ N ₄ were measured by UV-VIS. Figure 3 shows that the band gap after recombination of gC ₃ N ₄ varies with that of thin-layer graphite phase carbon nitride-doped graphene. The amount of thin-layer graphite phase carbon nitride increases and decreases, so the photocatalyst can be greatly increased and the light can be used.

The X-ray Photoelectron Spectroscopy (XPS) was used to analyze 行兩two-dimensional materials料 chemical bonding between layers. Figure 4 shows an absorption intensity at 286.7 eV. The absorption position is compared to the CN bonding signal. However, solid-phase graphite phase carbon nitride or a mixture of mixed graphite-phase carbon nitride and doped graphene does not have CN Bonding signal. From the above results, it can be known that the growth of thin-layer structure gC ₃ N ₄ on the doped graphene material by gas-phase 沈 deposition method will form a bond between the thin-layer gC ₃ N ₄ and the Doped Graphene laminated structure, by This changes the energy gap structure of the composite material.

Example 5: Photocatalytic photolysis of water to produce hydrogen

Experiment with the photolysis hydrogen production system. 10 mg of the photocatalyst of the examples and the comparative examples was added to 30 ml of water to form a mixed solution, the photocatalyst mixed solution was put into the reactor and H ₂ PtCl ₆ (3 wt%) was added. During the test, always keep stirring and turn on the cooling water to keep the reaction system at room temperature. Vacuum to remove all the gas in the system, turn on the light source (300W xenon lamp) for photocatalytic reaction for one hour. The hydrogen produced by the reaction was measured with an online gas chromatography analyzer. The results are shown in Figure 5.

Figure 5 is Comparative Example 1-solid-phase graphite phase carbon nitride, physical mixing and mixed-fired graphite phase carbon nitride-20wt% nitrogen-doped graphene and Example 5-thin-layer graphite phase carbon nitride-20wt% nitrogen-doped Graphene hydrogen production activity. It shows that the hydrogen production activity of thin-layer graphite phase carbon nitride-doped graphene photocatalyst is significantly better than that of bulk, physically mixed and mixed-fired graphite phase carbon nitride-20wt% nitrogen-doped graphene.

Example 6: Preparation of boron-doped graphene

Boric acid is used as a boron doping precursor. Graphene oxide and boric acid are mixed. Under an argon atmosphere, the temperature is raised to 600-900°C for 2-4 hours. The heating rate is controlled at 1-10°C/min. Fully react with graphene oxide powder. After natural cooling, the product is obtained and washed with deionized water at 60-80°C. After filtering, it is dried in an oven at 60-80°C to obtain boron-doped graphene powder. X-ray photoelectron spectroscopy (XPS) measured boron content of about 4.7 atomic%.

Example 7: Preparation of phosphorus-doped graphene

Phosphoric acid is used as a phosphorus doping precursor. Graphene oxide and phosphoric acid are mixed. Under an argon atmosphere, the temperature is raised to 600-900°C for 2-4 hours. The heating rate is controlled at 1-10°C/min. Fully react with graphene oxide powder, obtain the product after natural cooling, wash with 60-80℃ deionized water, filter and dry in 60-80℃ oven to obtain phosphorus-doped graphene powder. X-ray photoelectron spectroscopy (XPS) measured phosphorus content of about 9.0 atomic%.

Example 8: Graphite phase carbon nitride-20wt% boron doped graphene photocatalyst

3mg of boron-doped graphene powder of Example 6 was dispersed in an aqueous solution by ultrasonic wave and dried, then placed in an alumina crucible and placed downstream in the tubular furnace, and 10g of urea was placed in another crucible and Placed upstream in the tube furnace. Argon gas was introduced into the tubular furnace, and the temperature at the upstream was 550°C and the temperature at the downstream was 350°C in a three-zone system, and the temperature was naturally lowered after being maintained for 4 hours. The solid precursor molecules are polymerized in the upstream crucible, and the gaseous precursors are polymerized in the tubular furnace outside the crucible. After the natural temperature is lowered, the sediment in the downstream crucible is taken and washed with deionized water, and then dried in an oven. A thin layer of graphite phase carbon nitride-20wt% boron-doped graphene photocatalyst can be obtained.

Example 9: Graphite phase carbon nitride-20wt% phosphorus-doped graphene photocatalyst

Take 3 mg of the phosphorus-doped graphene powder of Example 7 dispersed in an aqueous solution by ultrasonic wave and dry it, place it in an alumina crucible and place it downstream in the tubular furnace, put 10 g of urea in another crucible and Placed upstream in the tube furnace. Argon gas was introduced into the tubular furnace, and the temperature at the upstream was 550°C and the temperature at the downstream was 350°C in a three-zone system, and the temperature was naturally lowered after being maintained for 4 hours. The solid precursor molecules are polymerized in the upstream crucible, and the gaseous precursors are polymerized in the tubular furnace outside the crucible. After the natural temperature is lowered, the sediment in the downstream crucible is taken and washed with deionized water, and then dried in an oven. A thin layer of graphite phase carbon nitride-20wt% phosphorus-doped graphene photocatalyst can be obtained.

Figure 6 uses UV-Visible to identify the thin-layer graphite phase carbon nitride-20wt% boron-doped graphene photocatalyst and thin-layer graphite phase carbon nitride-20wt% phosphorus-doped graphene photocatalyst of Examples 8 and 9. Graphite phase carbon nitride photocatalyst for comparison. The results show that the thin layer graphite phase carbon nitride-20wt% boron-doped graphene photocatalyst and the thin layer graphite phase carbon nitride-20wt% phosphorus-doped graphene photocatalyst have a band gap compared to the thin layer graphite phase Carbon nitride is lower, so it can increase the light utilization rate of the photocatalyst. Therefore, by vapor-depositing a thin layer of graphite phase carbon nitride on the graphene doped with heterogeneous elements, the heterogeneous atoms doped with graphene are bonded between the two-dimensional material layers to form a catalyst material with adjustable energy gap.

Photoluminescence (PL) spectroscopy is the result of the recombination of electron-hole pairs. It can be used to study the transfer and reorganization of electron-hole pairs. A decrease in the recombination rate of the electron hole pair will reduce the luminous intensity, which means that the photocatalytic activity is higher. Figure 7 is a PL diagram of different composition catalysts (thin-layer graphite phase carbon nitride, and thin-layer graphite phase carbon nitride-boron, phosphorus-doped graphene photocatalyst) with an excitation wavelength of 350 nm. The spectrum shows thin-layer graphite Compared with the thin layer graphite phase carbon nitride, the phase carbon nitride-20wt% boron doped graphene photocatalyst and the thin layer graphite phase carbon nitride-20wt% phosphorous doped graphene photocatalyst have lower intensity.

Comparing the single layer gC ₃ N ₄ single material 料PL spectrum before uncompositing, the results show that the thin layer of gC ₃ N ₄ can reduce the carrier recombination ratio. This is because the thin layer of gC ₃ N ₄ formed by vapor deposition has fewer defects And after the structure is thinned, the electrons move from the material 料 inside to the surface distance 離 is short, reducing the conduction of carriers between the multi-layer structures and causing the recombination mechanism 率. By further comparison, the PL spectra of thin-layer gC ₃ N ₄ and thin-layer graphene-doped hetero-element graphene composite materials show that thin-layer graphene-doped hetero-element graphene composite materials can further reduce the carrier recombination ratio. The composite material made by chemical vapor deposition料 can form a more uniform composite material料, the electron易 is transferred from gC ₃ N ₄ to the doped graphene, which effectively reduces the electronic electricity洞 and the combined fluorescent signal shows the quality element The existence of can promote the charge transfer between 兩two-dimensional materials料 interface. In addition, from the results, it can be seen that the properties of the two layers 狀 material 料 interfacial element and the bonds formed between them can improve the electronic and electrical 洞 shuttle between the interfaces to prolong the life of the charge carriers and improve the photocatalytic efficiency 率.

Although this disclosure has been disclosed as above with preferred embodiments, it is not intended to limit this disclosure. Anyone with ordinary technical knowledge in the art can make some changes and substitutions without violating the spirit and scope of this disclosure, so The scope of protection of this disclosure shall be subject to the scope defined in the appended patent application.

no.

FIG. 1A shows an X-ray diffraction (XRD) analysis diagram according to a comparative example of the present disclosure. FIG. 1B shows an XRD analysis diagram according to an embodiment of the present disclosure. FIG. 2A is a transmission electron microscope (TEM) diagram according to a comparative example of the present disclosure. FIG. 2B shows a TEM image according to an embodiment of the present disclosure. FIG. 3 shows an energy gap diagram according to an embodiment of the present disclosure. FIG. 4 is a graph of binding energy and strength according to an embodiment of the present disclosure. FIG. 5 is a graph showing hydrogen production activity according to an embodiment and a comparative example of the present disclosure. FIG. 6 shows an energy gap diagram according to an embodiment of the present disclosure. Figure 7 shows a photoluminescence spectrum according to an embodiment of the present disclosure.

Claims (23)

A graphite phase carbon nitride-doped heteroelement graphene photocatalyst, comprising: a graphene doped with heteroelement; and a graphite phase carbon nitride, wherein the graphene doped heteroelement and the graphite phase carbon nitride There is a chemical bond between them. The graphite phase carbon nitride-doped heteroelement graphene photocatalyst as described in item 1 of the patent application scope, wherein the chemical bond between the heteroelement and the graphite phase carbon nitride is an sp ³ bond. The graphite phase carbon nitride-doped heteroelement graphene photocatalyst as described in item 1 of the patent application scope, wherein the graphite phase carbon nitride has a thin layer structure. The graphite phase carbon nitride-doped heteroelement graphene photocatalyst as described in item 3 of the patent application scope, wherein the thickness of the thin layer structure is 0.3-4 nm. The graphite phase carbon nitride-doped heteroelement graphene photocatalyst as described in item 3 of the patent application scope, wherein the number of the thin layer structure layer is 1-12 layers. The graphite phase carbon nitride-doped heteroelement graphene photocatalyst as described in item 1 of the patent application scope, wherein the doped heteroelement is nitrogen, boron, phosphorus, sulfur, chlorine or bromine. The graphite phase carbon nitride-doped hetero-element graphene photocatalyst as described in item 1 of the patent application scope, wherein the ratio of the doped hetero-element to the graphene is 1-20 atomic%. The graphite phase carbon nitride-doped heteroelement graphene photocatalyst as described in item 1 of the patent application scope, wherein the ratio of the doped heteroelement graphene to the graphite phase carbon nitride is 1-40 wt%. The graphite phase carbon nitride-doped heteroelement graphene photocatalyst as described in item 1 of the scope of the patent application, wherein the ratio of the doped heteroelement graphene to the graphite phase carbon nitride is 5-20 wt%. The graphite phase carbon nitride-doped heteroelement graphene photocatalyst as described in item 1 of the patent application scope, wherein the catalyst has an energy gap between 1.6 and 2.8 eV. A method for manufacturing graphite phase carbon nitride-doped heterogeneous element graphene photocatalyst, comprising: providing a carrier gas into a reaction tank; providing a carbon nitride precursor upstream of the flow path of the carrier gas; providing a doping The heterogeneous element graphene is downstream of the flow path of the carrier gas; and the gasification of the carbon nitride precursor is heated to become a gas phase carbon nitride precursor, so that the gas phase carbon nitride precursor flows from the carrier gas flow path It moves upstream to downstream, and deposits the gas-phase carbon nitride precursor on the doped graphene to form a catalyst. The method for manufacturing graphene photocatalyst as described in item 11 of the patent application scope, wherein the heterogeneous element is nitrogen, boron, phosphorus, sulfur, chlorine, fluorine or bromine. The manufacturing method of graphene photocatalyst as described in Item 11 of the patent application scope, wherein the source of the heterogeneous element is 尿 element, 硫 urea, ammonia gas, boric acid, ammonium borate, 硫 acid, 硫 hydrogen chloride, phosphoric acid, ammonium chloride, ammonium fluoride, Ammonium bromide or its derivatives. The method for manufacturing graphene photocatalyst as described in item 11 of the patent application scope, wherein the ratio of the doped heteroelement to the graphene is 1-20 atomic%. The method for manufacturing graphene photocatalyst as described in item 11 of the patent application scope, wherein the mass ratio of the doped graphene to the carbon nitride precursor is 0.1-20 wt%. The manufacturing method of graphene photocatalyst as described in item 11 of the patent application scope, wherein the ratio of the heterogeneous element graphene to the graphite carbon nitride is 1-40wt%. The method for manufacturing graphene photocatalyst as described in item 11 of the patent application scope, wherein the carbon nitride precursor comprises melamine, melamine, monocyanamide, urea, thiourea, ammonia gas, and polyethylene polyamine Or its derivatives. The method for manufacturing graphene photocatalyst as described in item 11 of the patent application scope, wherein the carbon nitride precursor may be solid, liquid or gas. The method for manufacturing graphene photocatalyst as described in item 11 of the patent application scope, wherein the carrier gas comprises nitrogen, argon, ammonia, hydrogen sulfide, or a combination of the foregoing. The manufacturing method of graphene photocatalyst as described in item 11 of the patent application scope, wherein the carrier gas flow rate is 1-100 ml/min. The method for manufacturing graphene photocatalyst as described in item 11 of the patent application scope, wherein the reaction temperature is between 350 and 900°C. The manufacturing method of graphene photocatalyst as described in item 11 of the patent application scope, wherein the pressure of the reaction tank is between 0 and 50 torr. The manufacturing method of graphene photocatalyst as described in item 11 of the patent application scope, wherein the doped heteroelement graphene is made of graphene monoxide and a compound containing heteroelement.

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