CN113289653A - g-C of load metal monoatomic3N4Method for preparing photocatalyst - Google Patents
g-C of load metal monoatomic3N4Method for preparing photocatalyst Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims description 14
- 229910001510 metal chloride Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 150000003841 chloride salts Chemical class 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims 2
- 229910052734 helium Inorganic materials 0.000 claims 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 2
- 238000004108 freeze drying Methods 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001257 hydrogen Substances 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000000354 decomposition reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000011161 development Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of energy materials and photocatalysis, and provides g-C loaded with metal monoatomic3N4A preparation method of the photocatalyst. g-C of the Supported Metal prepared according to the invention3N4The photocatalyst is a brand new photocatalyst, has more active sites and N sites with lower electron density, and the synergistic effect of the active sites and the N sites ensures higher electron-hole separation so as to enhance the activity of photocatalytic decomposition of water to produce hydrogen. Comparison of pure g-C without Metal Supported3N4And hydro-thermal synthesis of metal-loaded g-C3N4Has higher catalytic activity.
Description
Technical Field
The invention belongs to the technical field of energy materials and photocatalysis, and particularly relates to g-C3N4As a carrier, metal chloride is used as a metal source, and the metal-doped M-g-C is synthesized by a two-step method of solution dispersion and calcination3N4A photocatalyst for producing hydrogen by efficiently photolyzing water and a preparation method thereof.
Background
Since the 20 th century, due to the rapid development of science and technology and industry, the rate of human energy use has increased year by year, with the development of energy consumption and industry, a great deal of energy and environmental problems have been brought about. Therefore, the development of a novel green energy source and a conversion technology which can be continuously developed becomes an urgent problem to be solved. The hydrogen produced by photolysis can utilize inexhaustible solar energy at normal temperature and pressureThe raw material water which is easily obtained in nature is converted into energy and chemical raw material H which can be utilized by human beings2So as to realize reasonable energy circulation and clean energy development, which are the focus of attention in recent years. However, the development of photocatalysts, photocatalytic water splitting to produce hydrogen and the like still faces a common challenge: the photocatalyst surface electron-hole recombination is severe. For this reason, researchers have conducted a number of experiments in catalyst development. g-C3N4/H2PtCl6Is the main hydrogen production system by decomposing water by photocatalysis at present, but because of g-C3N4Extremely high electron-hole recombination, high cost of noble metal Pt, poor visible light absorptivity of the catalyst and the like, and cannot be applied on a large scale. Therefore, the development of low electron-hole recombination, Pt-free systems for photocatalysis is imminent.
Research shows that metal atoms are doped with g-C3N4Such as Fe, Co, Ni, Rh, Ru and the like, has high catalytic potential for photocatalytic water splitting to produce hydrogen. And have been extensively studied because of their low cost and their relative contribution to electron-hole separation. The main reasons for improving the hydrogen production by photocatalytic water decomposition by metal atom doping are as follows: by doping metals to g-C3N4In addition, the metal atom changes C, N electron cloud density, is beneficial to electron-hole separation and simultaneously enhances g-C3N4The adsorption to water molecules is beneficial to transferring electrons to reactant water molecules. Such as Chen Zhiwei et al [ Chen Z.appl.Catal.B-environ.2020,274:119117.]It was found that g-C supporting Rh atoms3N4The evolution potential of H is reduced and the free charge transfer capability is enhanced, thereby enhancing the catalytic activity. Cao Yuanjie et al [ Cao Y. Angew. chem. int. Ed.2017,56: 12191-.]Research shows that Co coordinated donor nitrogen increases electron density and lowers formation barrier of key cobalt hydride intermediate, thereby accelerating H-H bond coupling and promoting H2And (4) generating. However, the preparation method of doping a large amount of efficient metal atoms is still relatively limited, and further development is needed to show a strategy. More importantly, the prior non-noble metal is doped with g-C3N4The catalytic activity of the photocatalyst is still low, and further one is requiredThe activity is improved.
Based on the above analysis, the present invention proposes to utilize the graphite phase carbon nitride g-C3N4The metal chloride salt is used as a metal source for catalyst and carrier, and the metal-doped M-g-C is synthesized by a two-step method of solution dispersion and calcination3N4A photocatalyst. We propose that this preparation strategy is based primarily on the following considerations: g-C3N4Has proper forbidden band width and is beneficial to H2Reducing O; at the same time g-C3N4The 3-s-triazine structure has a large number of coordination sites which are beneficial to chelating metal atoms. The metal salt is dissolved in the solvent water and can be uniformly dispersed to g-C3N4In the high-temperature calcination process, the metal chloride salt has a lower melting point and becomes molten, so that the metal chloride salt has higher polarity compared with liquid phase deposition and is easier to react with g-C3N4Chelating the coordination site. Compared with liquid phase deposition and light deposition, the method has higher catalytic activity and stability, is simple, green and pollution-free, can be used for large-scale production, and is an ideal photocatalyst preparation method.
Disclosure of Invention
g-C of load metal monoatomic3N4The photocatalyst and the preparation method. In g-C3N4The metal chloride is used as a metal source for the catalyst and the carrier, and the photocatalyst loaded with metal is synthesized by a two-step method of solution dispersion and calcination. In the solvent dispersion process, the metal chloride salt is uniformly dispersed to g-C3N4On the powder, metal and g-C in the calcining process are facilitated3N4And (4) coordination. High temperature calcination of metals to g-C using the polarity of the metal chloride salt3N4The site is chelated, and the structure of M-N4 after coordination changes g-C3N4The electron density of the N is high, and the separation of electron and hole is facilitated, so that the hydrogen production by photocatalytic water decomposition is promoted.
The technical scheme of the invention is as follows:
g-C of load metal monoatomic3N4The preparation method of the photocatalyst comprises the following steps:
(1) preparation of Metal doped g-C3N4A photocatalyst precursor; g to C3N4Dispersing the powder in the solution, adding metal chloride salt to obtain a mixed solution A, wherein g-C3N4The mass concentration of (A) is 0.01-1g mL-1(ii) a The mass concentration of the metal chloride salt is 0.01-0.1g mL-1. After being stirred evenly, the mixed solution A is transferred into a reaction container, and after being dried, the mixed solution A is post-treated to obtain metal doped g-C3N4Catalyst precursor M-g-C3N4。
(2) Doping the metal obtained in the step 1) with g-C3N4Photocatalyst precursor M-g-C3N4And (3) placing the mixture in a tubular furnace, heating the mixture from room temperature to a calcination temperature, and calcining the mixture at the high temperature of 200-500 ℃ for 1-8 hours to obtain solid powder A.
(3) Cleaning and filtering the solid powder A obtained in the step 2) to obtain the photocatalyst M-g-C3N4。
M in the step 1) is one or the combination of more than two of chromium, manganese, iron, cobalt, nickel and ruthenium.
The high-temperature calcining atmosphere in the step 2) can be one or more of inert gas (nitrogen, argon and the like), air, hydrogen and the like.
The temperature rise rate in the step 2) is 1-20 ℃ min-1
g-C of load metal monoatomic3N4The photocatalyst is prepared by the preparation method. Obtaining M-g-C3N4Is a 3 s-triazine structure of M-N4. Fluorescence spectrum shows that the product is relatively pure g-C3N4Has better electron-hole separation capability, and has a g-C ratio in the reaction of photocatalytic decomposition of water to produce hydrogen3N4Better catalytic performance
The invention has the beneficial effects that:
1) M-g-C prepared by the invention3N4Due to the structure of M-N4, the photocatalyst can effectively reduce electron-hole recombination and is beneficial to photocatalytic water decomposition to produce hydrogen.
2) The high dispersion of the metal provides more active sites, further promoting the reaction of photocatalytic decomposition of water to produce hydrogen.
3) The metal is the synergistic effect between nitrogen, promotes the electron transfer between the catalyst and water, and is beneficial to the photocatalytic decomposition of water to produce hydrogen.
4) M-g-C of the present invention3N4The activity and stability of the catalyst in TEOA solution are far higher than those of pure g-C3N4Hydro-thermal synthesis of g-C loaded with metals3N4。
5) The catalyst provided by the invention has the advantages of low toxicity of selected reagents, wide source of raw materials, low cost, simple preparation process, greenness, no pollution, easiness in scale-up production and contribution to scale application.
Drawings
FIG. 1 is pure g-C3N4Scanning electron microscope pictures.
FIG. 2 shows Co in example0.1-g-C3N4-350-3 scanning electron microscope pictures.
FIG. 3 is pure g-C3N4And example Co0.1-g-C3N4-350-3XRD contrast pictures.
FIG. 4 is pure g-C3N4And example Co0.1-g-C3N4-350-3 fluorescence spectra picture.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example (b):
1g g-C3N4With 0.1g of CoCl2·6H2Mixing O uniformly, adding 50mL of deionized water, stirring for four hours to obtain a mixed solution A, drying the mixed solution A in an oven at 60 ℃ for 10 hours, and grinding to obtain M-g-C3N4Precursor Co/g-C3N4。
Mixing Co/g-C3N4The precursor is put into a tube furnace at N2Calcining for 3h in the atmosphere, wherein the calcining temperature is 350 ℃, and the heating rate is 5 ℃/min. Washing and filtering the obtained solid powder by using 100mL of deionized water to finally obtain Co0.1-g-C3N4-350-3(Co0.1-g-C3N40.1 in-350-3 represents CoCl.6H in the raw Material2The mass fraction of O is 0.1, 350 represents that the calcination temperature is 350 ℃, and 3 represents that the calcination temperature is 3 h). And then carrying out photocatalytic hydrogen production performance test. The hydrogen production performance is increased along with the increase of the metal amount, and the performance reaches the best at 10 wt%. The hydrogen production rate in TEOA (10%) aqueous solution is 2.1mmol g-1h-1Relatively pure g-C3N40.03mmol g-1h-1The method is greatly improved.
The above-mentioned embodiments are preferred embodiments of the present invention, and are intended to enable those skilled in the art to understand the main contents of the present invention and implement the present invention, but the present invention is not limited to the above-mentioned embodiments. All modifications, combinations, and simplifications which may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. g-C of load metal monoatomic3N4The preparation method of the photocatalyst is characterized by comprising the following steps:
(1) preparation of Metal doped g-C3N4A photocatalyst precursor; g to C3N4Dispersing the powder in the solution, adding metal chloride salt to obtain a mixed solution A, wherein g-C3N4The mass concentration of (A) is 0.01-1g mL-1(ii) a The mass concentration of the metal chloride salt is 0.01-0.1g mL-1(ii) a After being stirred uniformly, the mixed solution A is transferred into a reaction container for drying and then post-treatment to obtain metal doped g-C3N4Photocatalyst precursor M-g-C3N4；
(2) Doping the metal obtained in the step 1) with g-C3N4Photocatalyst precursor M-g-C3N4Placing the mixture in a tubular furnace, and heating the mixture from room temperature to a calcination temperature under an inert atmosphere for high-temperature calcination, wherein the calcination temperature is 200-500 ℃ and the calcination time is 1-8 h, so as to obtain solid powder A;
(3) solid powder obtained in step 2)Cleaning and filtering the powder A to obtain the photocatalyst M-g-C3N4。
2. The metal monoatomic supported g-C according to claim 13N4The preparation method of the photocatalyst is characterized in that M in the step 1) comprises one or the combination of more than two of chromium, manganese, iron, cobalt, nickel and ruthenium.
3. A metal monoatomic supported g-C according to claim 1 or 23N4The preparation method of the photocatalyst is characterized in that the drying mode in the step 1) is freeze drying, air oven drying or vacuum drying.
4. A metal monoatomic supported g-C according to claim 1 or 23N4The preparation method of the photocatalyst is characterized in that the inert atmosphere in the step 1) is one or the combination of more than two of nitrogen, argon and helium.
5. A metal monoatomic supported g-C according to claim 33N4The preparation method of the photocatalyst is characterized in that the inert atmosphere in the step 1) is one or the combination of more than two of nitrogen, argon and helium.
6. A metal monoatomic supported g-C according to claim 1, 2 or 53N4The preparation method of the photocatalyst is characterized in that the temperature rise rate in the step 2) is 1-10 ℃ for min-1。
7. A metal monoatomic supported g-C according to claim 33N4The preparation method of the photocatalyst is characterized in that the temperature rise rate in the step 2) is 1-10 ℃ for min-1。
8. A metal monoatomic supported g-C according to claim 43N4The preparation method of the photocatalyst is characterized in that the temperature rise rate in the step 2) is 1-10 ℃ for min-1。
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| CN113856735A (en) * | 2021-11-23 | 2021-12-31 | 廊坊师范学院 | Composite photocatalyst and preparation method and application thereof |
| CN114054066A (en) * | 2021-11-30 | 2022-02-18 | 江苏大学 | Doped g-C3N4Nanotube photocatalyst, preparation method and application |
| CN114130387A (en) * | 2021-11-26 | 2022-03-04 | 合肥智慧环境研究院 | Nitrogen-defect g-C3N4 surface-doped nano-manganese catalyst and preparation method and application thereof |
| CN114210328A (en) * | 2021-12-29 | 2022-03-22 | 江苏大学 | Rh monoatomic-modified PCN photocatalyst and preparation method and application thereof |
| CN114452998A (en) * | 2022-01-26 | 2022-05-10 | 大连理工大学 | Preparation method and application of multi-walled carbon nanotube and graphitized carbon nitride composite material |
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| CN115805091A (en) * | 2022-10-19 | 2023-03-17 | 重庆大学 | Preparation method of copper-silver double-monoatomic photocatalyst |
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