CN111359652A - Carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof - Google Patents
Carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
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- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
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- 238000000870 ultraviolet spectroscopy Methods 0.000 description 18
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 10
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention discloses a carbon nitride-based nickel-gold bimetallic supported catalyst and a preparation method thereof3N4) A substrate, then g-C3N4Dispersing in ultrapure water, mixing with hole sacrificial agent, nickel chloride solution and chloroauric acid solution, and irradiating with xenon lamp to deposit metal nickel and gold on g-C3N4A surface. The catalyst prepared by the invention shows more excellent catalytic performance than the same type of catalyst in a 4-NP (sodium borohydride) reduction experiment, wherein the highest catalytic efficiency is achieved when the Au content is 1 wt% and the Ni content is 8 wt%, and the catalytic performance reaches 3.3928min‑1. The catalyst has the synergistic effect of the nickel and gold bimetal during the catalysis process, and greatly improvesCatalytic performance. In the catalyst preparation experiment, the usage amount of the noble metal Au is only 1 wt%, the usage amount of the relatively cheap non-noble metal Ni is 15 wt% at most, and the preparation cost is reduced on the premise of ensuring high catalytic performance.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a carbon nitride-based nickel-gold bimetallic supported catalyst and a preparation method thereof.
Background
P-nitrophenol, also known as 4-nitrophenol (4-NP), is an organic pollutant widely existing in industrial production wastewater of petrifaction, textile, metallurgy, paper making and the like, and the substance has high solubility and stability in water, so that the substance becomes one of water pollutants which are difficult to treat.
Sodium borohydride reduces p-nitrophenol (4-NP) to obtain important industrial intermediate 4-aminophenol (4-AP) is considered to be an effective method for treating 4-NP, the method is simple to operate, safe and pollution-free, 4-NP can be completely converted into 4-AP, no by-product is generated, but the reaction needs to be carried out by adding a catalyst, and therefore, the research on the catalyst for effectively degrading 4-NP is of great significance.
g-C3N4Is a graphite-like layered polymer semiconductor material consisting of C, N two elements. C, N are connected by chemical bonds, so that functional groups with high reactivity are absent, the functional groups can stably exist at a high temperature of 400 ℃ for a long time, and can not be decomposed under the conditions of acid-base (pH is 0-14) and organic solvents, so that the functional groups have good thermal stability and chemical stability; g-C3N4The specific surface area of the catalyst is larger, rich anchoring sites are provided for the load of metal nano particles, and the catalyst can be used as an excellent carrier of the catalyst, so g-C is selected3N4As a carrier, stable and efficient g-C can be prepared by depositing noble metal nano-particles through environment-friendly photochemistry3N4A base catalyst.
Since the supported Au nanoparticles have ultrahigh oxidation activity to CO at low temperature, the Au nanoparticles have proved to be efficient catalysts in various catalytic reaction processes, such as reduction catalysis of nitrogen oxides, acetylene hydrochlorination reaction, catalytic nitrophenol reduction and synthesis of various organic substances.
However, Au is expensive and has a high cost when used for manufacturing the catalyst, while Ni is a non-noble metal and has a low price, so that gold and nickel are introduced as the bimetallic catalyst, on one hand, the cost of the catalyst can be greatly reduced, and on the other hand, the bimetallic catalyst has a synergistic effect and can often show more excellent catalytic reaction performance compared with a single-metal component catalyst.
Chinese patent application publication No. CN106902829B, published as 2019-08-23, entitled "a supported bimetallic reforming catalyst and a preparation method and application thereof", discloses a high-activity bimetallic methane and carbon dioxide reforming catalyst, and solves the problems of poor carbon deposit resistance, complex preparation method, high catalyst cost and the like of the existing catalyst.
The invention provides the carbon nitride-based nickel-gold bimetallic supported catalyst prepared by the environment-friendly photo-deposition method, and the catalyst has the advantages of excellent performance, high stability, low cost and greatly widened application prospect.
Disclosure of Invention
The invention aims to solve the defects of the existing catalyst and provides a nickel and gold bimetal which has a synergistic effect in the catalytic process, the catalytic performance is strong, and the catalytic efficiency can reach 3.3928min at most-1Compared with the existing catalyst preparation method, the preparation method has the advantages of simple and easily-controlled production process, energy conservation, environmental protection, no need of adding other toxic reagents, and environmental friendliness.
In order to achieve the purpose, the invention adopts the following technical scheme:
carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof, and catalystThe agent takes carbon nitride as a substrate and urea as a precursor to synthesize g-C3N4The preparation method of the catalyst comprises the following steps:
(1) calcining urea at 500-600 ℃ for more than 2 hours in air atmosphere to obtain a solid sample, and fully grinding the solid sample to obtain solid powder;
(2) annealing the obtained solid powder at 550 deg.C for more than 30 min under air atmosphere to obtain g-C3N4A solid powder;
(3) taking a certain mass of g-C3N4Dispersing the solid powder in deionized water, and performing ultrasonic treatment for more than 4 hours to obtain g-C3N4A suspension;
(4) in g-C3N4Adding cavity sacrificial agent and chloroauric acid solution (HAuCl) into the suspension4·3H2O) and nickel chloride solution (NiCl)2·6H2O), obtaining a mixed solution, and uniformly stirring;
(5) irradiating the mixed solution with xenon lamp for 2 hr, washing with deionized water and alcohol for several times, vacuum drying at 40 deg.C for 24 hr to obtain Ni/Au-g-C3N4A catalyst.
Preferably, in the mixed solution of step (4), Au element and g-C3N4The mass ratio is 1: 100.
preferably, the mass ratio of the Au element to the Ni element is 1: (1-15).
Preferably, in the step (1), the urea is put in a crucible with a cover and calcined at 550 ℃ for 120min in an air atmosphere, and the heating rate is 10 ℃/min.
Preferably, in the step (2), the solid powder is annealed in a crucible with a cover at 550 ℃ for 30 minutes in an air atmosphere, and the temperature increase rate is 10 ℃/min.
Preferably, the cavity sacrificial agent is at least one of isopropanol, tert-butanol, methanol, triethanolamine, lactic acid, sodium sulfide, sodium sulfite and ammonium oxalate.
Preferably, in the step (5), the deionized water and the alcohol are washed at least three times respectively.
Preferably, the xenon lamp power is 300W, the irradiation time is 2 hours, the xenon lamp is used for irradiation, the reaction process is continuously stirred, and the reaction temperature is maintained at 20 ℃, so that the metal nickel and the metal gold are deposited in g-C3N4A surface.
The invention has the following remarkable advantages:
1) the nickel and gold bimetal play a synergistic role in the catalysis process of the carbon nitride-based nickel-gold bimetal supported catalyst prepared by the invention, and the catalysis performance can be greatly improved. The catalyst prepared by the invention shows more excellent catalytic performance than the same type of catalyst in a 4-NP (sodium borohydride) reduction experiment by catalyzing, and the highest catalytic efficiency is 3.3928min-1。
2) The catalyst adopts lower usage amount (1 wt%) of noble metal Au and higher usage amount (15 wt%) of non-noble metal Ni, and the preparation cost is reduced on the premise of ensuring high catalytic performance.
3) Compared with the existing catalyst preparation method, the preparation method adopted by the invention has the advantages of simple and easily-controlled production process, energy conservation, environmental protection, no need of adding other toxic reagents, greenness and no pollution.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of samples obtained from examples 1 and 2;
FIG. 2 is a Transmission Electron Microscope (TEM) image of a sample obtained in example 4;
FIG. 3 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 1;
FIG. 4 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 2;
FIG. 5 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 3;
FIG. 6 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 4;
FIG. 7 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 5;
FIG. 8 is an ultraviolet-visible absorption spectrum (UV-VIS) image of example 6;
fig. 9 is a graph of catalytic efficiency of the catalytic results of examples 1-6 after fitting with a pseudo-first order kinetic model.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1:
12g of urea is weighed and placed in a crucible with a cover, and calcined for 120 minutes at 550 ℃ in air atmosphere, and the heating rate is 10 ℃/min. The obtained solid was fully ground and then calcined again at 550 ℃ for 30 minutes in an air atmosphere at a heating rate of 10 ℃/min. Grinding the obtained light yellow solid to obtain the required carbon nitride (g-C)3N4)。
0.2g of carbon nitride powder is weighed into 80mL of deionized water, and ultrasonic dispersion is carried out for 4 hours to obtain g-C3N4And (3) suspension. To the suspension was added 2mL of isopropanol and stirred well. Then 1mL of chloroauric acid (HAuCl) with a concentration of 4g/L was added to the suspension4·3H2O) solution and 10mL of nickel chloride (NiCl) with a concentration of 6.815mmol/L2·6H2O) solution and stirred uniformly (Au content 1 wt% of carbon nitride and Ni content 2 wt% of carbon nitride).
The above mixed liquid was irradiated under a 300W xenon lamp for 2 hours while the reaction was continuously stirred and the reaction temperature was maintained at 20 ℃. Centrifuging to separate out solid after illumination is finished, respectively cleaning with deionized water and alcohol for three times, vacuum drying at 40 deg.C for 24 hr, and labeling with Ni2Au1-CN。
Fig. 1 is an X-ray diffraction (XRD) pattern of examples 1 and 2, with 2 θ of 27.6 ° and 13.0 ° assigned to g-C, respectively3N4(002) Diffraction peaks for the (100) and (2) crystal planes, demonstrating the presence of graphite phase carbon nitride, and no significant shift of the main peak is observed at 27.6 °, indicating that the deposition of gold and nickel does not alter the crystal structure of the carbon nitride; 2 θ ═ 38.2 ° and 44.4 ° are diffraction peaks assigned to the Au (111) crystal plane and the (200) crystal plane, respectively, and demonstrate deposition of Au on the surface of carbon nitride; no characteristic diffraction peak of Ni was observed in all samples, indicating that the Ni nanoparticles are very small and highly dispersed on the surface of the carbon nitride;
FIG. 3 is a drawing showingExample 1 image of catalytic reaction under ultraviolet-visible spectrophotometer (UV-VIS) monitoring. The whole catalytic reaction is completed within 4 minutes, and the reaction rate (Kapp) after pseudo first-order kinetic model fitting is 0.9522min-1
Example 2:
12g of urea is weighed and placed in a crucible with a cover, and calcined for 120 minutes at 550 ℃ in air atmosphere, and the heating rate is 10 ℃/min. The obtained solid was fully ground and then calcined again at 550 ℃ for 30 minutes in an air atmosphere at a heating rate of 10 ℃/min. Grinding the obtained light yellow solid to obtain the required carbon nitride (g-C)3N4)。
0.2g of carbon nitride powder is weighed into 80mL of deionized water, and ultrasonic dispersion is carried out for 4 hours to obtain g-C3N4And (3) suspension. To the suspension was added 2mL of isopropanol and stirred well. Then 1mL of chloroauric acid (HAuCl) with a concentration of 4g/L was added to the suspension4·3H2O) solution and 10mL of nickel chloride (NiCl) with a concentration of 17.04mmol/L2·6H2O) solution and stirred uniformly (Au content 1 wt% of carbon nitride, Ni content 5 wt% of carbon nitride).
The above mixed liquid was irradiated under a 300W xenon lamp for 2 hours while the reaction was continuously stirred and the reaction temperature was maintained at 20 ℃. Centrifuging to separate out solid after illumination is finished, respectively cleaning with deionized water and alcohol for three times, vacuum drying at 40 deg.C for 24 hr, and labeling with Ni5Au1-CN。
FIG. 4 is an image of the catalytic reaction of example 2 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS), the whole catalytic reaction is completed within 4 minutes, and the reaction rate (Kapp) after fitting of a pseudo-first order kinetic model is 1.2984min-1。
Example 3:
12g of urea is weighed and placed in a crucible with a cover, and calcined for 120 minutes at 550 ℃ in air atmosphere, and the heating rate is 10 ℃/min. The obtained solid was fully ground and then calcined again at 550 ℃ for 30 minutes in an air atmosphere at a heating rate of 10 ℃/min. Grinding the obtained light yellow solid to obtain the required carbon nitride (g-C)3N4)。
0.2g of carbon nitride powder is weighed into 80mL of deionized water, and ultrasonic dispersion is carried out for 4 hours to obtain g-C3N4And (3) suspension. To the suspension was added 2mL of isopropanol and stirred well. Then 1mL of chloroauric acid (HAuCl) with a concentration of 4g/L was added to the suspension4·3H2O) solution and 10mL of 27.26mmol/L nickel chloride (NiCl)2·6H2O) solution and stirred uniformly (Au content 1 wt% of carbon nitride, Ni content 8 wt% of carbon nitride).
The above mixed liquid was irradiated under a 300W xenon lamp for 2 hours while the reaction was continuously stirred and the reaction temperature was maintained at 20 ℃. Centrifuging to separate out solid after illumination is finished, respectively cleaning with deionized water and alcohol for three times, vacuum drying at 40 deg.C for 24 hr, and labeling with Ni8Au1-CN。
FIG. 5 is an image of the catalytic reaction of example 3 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS). The whole catalytic reaction is completed within 2 minutes, and the reaction rate (Kapp) after pseudo first-order kinetic model fitting is 3.3928min-1。
Example 4:
12g of urea is weighed and placed in a crucible with a cover, and calcined for 120 minutes at 550 ℃ in air atmosphere, and the heating rate is 10 ℃/min. The obtained solid was fully ground and then calcined again at 550 ℃ for 30 minutes in an air atmosphere at a heating rate of 10 ℃/min. Grinding the obtained light yellow solid to obtain the required carbon nitride (g-C)3N4)。
0.2g of carbon nitride powder is weighed into 80mL of deionized water, and ultrasonic dispersion is carried out for 4 hours to obtain g-C3N4And (3) suspension. To the suspension was added 2mL of isopropanol and stirred well. Then 1mL of chloroauric acid (HAuCl) with a concentration of 4g/L was added to the suspension4·3H2O) solution and 10mL of 34.08mmol/L nickel chloride (NiCl)2·6H2O) solution and stirred uniformly (Au content 1 wt% of carbon nitride, Ni content 10 wt% of carbon nitride).
The above mixed liquid was irradiated under a 300W xenon lamp for 2 hours while the reaction was continuously stirred and the reaction temperature was maintained at 20 ℃. Centrifuging to separate out after illuminationWashing the solid with deionized water and alcohol for three times, vacuum drying at 40 deg.C for 24 hr, and labeling with Ni10Au1-CN。
FIG. 2 is a Transmission Electron Microscope (TEM) image of the sample obtained in example 4. The figure shows that the carbon nitride substrate has a layered structure, and the Ni and Au bimetallic catalysts are uniformly loaded on the surface of the carbon nitride;
FIG. 6 is an image of the catalytic reaction of example 4 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS), the whole catalytic reaction is completed within 3 minutes, and the reaction rate (Kapp) after fitting of a pseudo-first order kinetic model is 1.6494min-1。
Example 5:
12g of urea is weighed and placed in a crucible with a cover, and calcined for 120 minutes at 550 ℃ in air atmosphere, and the heating rate is 10 ℃/min. The obtained solid was fully ground and then calcined again at 550 ℃ for 30 minutes in an air atmosphere at a heating rate of 10 ℃/min. Grinding the obtained light yellow solid to obtain the required carbon nitride (g-C)3N4)。
0.2g of carbon nitride powder is weighed into 80mL of deionized water, and ultrasonic dispersion is carried out for 4 hours to obtain g-C3N4And (3) suspension. To the suspension was added 2mL of isopropanol and stirred well. Then 1mL of chloroauric acid (HAuCl) with a concentration of 4g/L was added to the suspension4·3H2O) solution and 10mL of nickel chloride (NiCl) with a concentration of 40.89mmol/L2·6H2O) solution and stirred uniformly (Au content 1 wt% of carbon nitride, Ni content 12 wt% of carbon nitride).
The above mixed liquid was irradiated under a 300W xenon lamp for 2 hours while the reaction was continuously stirred and the reaction temperature was maintained at 20 ℃. Centrifuging to separate out solid after illumination is finished, respectively cleaning with deionized water and alcohol for three times, vacuum drying at 40 deg.C for 24 hr, and labeling with Ni12Au1-CN。
FIG. 7 is an image of the catalytic reaction of example 5 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS), the whole catalytic reaction is completed within 4 minutes, and the reaction rate (Kapp) after fitting of a pseudo-first order kinetic model is 1.3575min-1。
Example 6:
12g of urea is weighed and placed in a crucible with a cover, and calcined for 120 minutes at 550 ℃ in air atmosphere, and the heating rate is 10 ℃/min. The obtained solid was fully ground and then calcined again at 550 ℃ for 30 minutes in an air atmosphere at a heating rate of 10 ℃/min. Grinding the obtained light yellow solid to obtain the required carbon nitride (g-C)3N4)。
0.2g of carbon nitride powder is weighed into 80mL of deionized water, and ultrasonic dispersion is carried out for 4 hours to obtain g-C3N4 suspension. To the suspension was added 2mL of isopropanol and stirred well. Then 1mL of chloroauric acid (HAuCl) with a concentration of 4g/L was added to the suspension4·3H2O) solution and 10mL of nickel chloride (NiCl) with a concentration of 51.11mmol/L2·6H2O) solution and stirred uniformly (Au content 1 wt% of carbon nitride, Ni content 15 wt% of carbon nitride).
The above mixed liquid was irradiated under a 300W xenon lamp for 2 hours while the reaction was continuously stirred and the reaction temperature was maintained at 20 ℃. Centrifuging to separate out solid after illumination is finished, respectively cleaning with deionized water and alcohol for three times, vacuum drying at 40 deg.C for 24 hr, and labeling with Ni15Au1-CN。
FIG. 8 is an image of the catalytic reaction of example 6 under the monitoring of an ultraviolet-visible spectrophotometer (UV-VIS), the whole catalytic reaction is completed within 4 minutes, and the reaction rate (Kapp) after fitting of a pseudo-first order kinetic model is 1.0656min-1。
FIG. 9 is a graph comparing the catalytic rates of examples 1-6 after fitting with a pseudo-first order kinetic model, from which it can be seen that the Au content is 1 wt%, the Ni content is increased from 1 wt% to 15 wt%, the catalytic rate is increased and then decreased, wherein when the Ni content is 8 wt%, the catalytic rate is the highest, and the catalytic efficiency is up to 3.3928min-1The nickel and gold bimetal play a synergistic role in the catalysis process of the carbon nitride-based nickel-gold bimetal supported catalyst prepared by the invention, and the catalysis performance can be greatly improved. The catalyst prepared by the invention shows more excellent catalytic performance than the same type of catalyst in a 4-NP (sodium borohydride) reduction experiment by catalyzing, and the catalyst adopts lower usage amount (1 wt%) of noble metal Au than AuCompared with the existing catalyst preparation method, the preparation method adopted by the invention has the advantages of simple and easily-controlled production process, energy conservation and environmental protection, no need of adding other toxic reagents, and no pollution.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (8)
1. A carbon nitride-based nickel-gold bimetallic supported catalyst and a preparation method thereof are characterized in that: the catalyst takes carbon nitride as a substrate and urea as a precursor to synthesize g-C3N4The preparation method of the catalyst comprises the following steps:
(1) calcining urea at 500-600 ℃ for more than 2 hours in air atmosphere to obtain a solid sample, and fully grinding the solid sample to obtain solid powder;
(2) annealing the obtained solid powder at 500-600 ℃ for more than 30 minutes under the air atmosphere condition to obtain g-C3N4A solid powder;
(3) taking a certain mass of g-C3N4Dispersing the solid powder in deionized water, and performing ultrasonic treatment for more than 4 hours to obtain g-C3N4A suspension;
(4) in g-C3N4Adding cavity sacrificial agent and chloroauric acid solution (HAuCl) into the suspension4·3H2O) and nickel chloride solution (NiCl)2·6H2O), obtaining a mixed solution, and uniformly stirring;
(5) irradiating the mixed solution with xenon lamp for more than 2 hr, centrifuging to separate out solid, washing with deionized water and alcohol for several times, vacuum drying at 40 deg.C for 24 hr to obtain Ni/Au-g-C3N4Catalyst and process for preparing same。
2. The Ni-based nitride-Au bimetallic supported catalyst and the preparation method thereof as claimed in claim 1, wherein in the mixed solution of step (4), Au element and g-C are added3N4The mass ratio is 1: 100.
3. the carbon nitride-based nickel-gold bimetallic supported catalyst and the preparation method thereof according to claim 2, wherein the mass ratio of the Au element to the Ni element is 1: (1-15).
4. The carbon nitride-based nickel-gold bimetallic supported catalyst and the preparation method thereof as claimed in claim 1, wherein in the step (1), the urea is calcined in a crucible with a cover at 550 ℃ for 120min in an air atmosphere, and the heating rate is 10 ℃/min.
5. The carbon nitride-based nickel-gold bimetallic supported catalyst and the preparation method thereof as claimed in claim 1, wherein in the step (2), the solid powder is annealed in a crucible with a cover at 550 ℃ for 30 minutes in an air atmosphere, and the heating rate is 10 ℃/min.
6. The Ni-Au bimetallic supported carbon nitride catalyst as claimed in claim 1, wherein the hole sacrificial agent is at least one of isopropanol, tert-butanol, methanol, triethanolamine, lactic acid, sodium sulfide, sodium sulfite, and ammonium oxalate.
7. The supported catalyst of claim 1, wherein in the step (5), the deionized water and the alcohol are washed at least three times respectively.
8. The Ni-based nitride-Au bimetallic supported catalyst and the preparation method thereof as claimed in claim 1, wherein the xenon lamp power is 300W, the irradiation time is 2 hours, the reaction process is continuously stirred and the reaction temperature is maintained at 20 ℃.
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