CN111250137A - Modified g-C for photocatalytic hydrogen production3N4Process for preparing catalyst - Google Patents
Modified g-C for photocatalytic hydrogen production3N4Process for preparing catalyst Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 117
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 14
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 13
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- -1 potassium ferricyanide Chemical compound 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000013082 iron-based metal-organic framework Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
-
- 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
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/28—Phosphorising
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- 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 relates to a modified g-C for photocatalytic hydrogen production3N4A method for preparing the catalyst. Synthesis of CoP/FeP/g-C by a simple Process3N4Heterostructures to enhance the electrochemical properties of photocatalysis. Firstly synthesizing a ZIF-67 cubic precursor, then growing a layer of Fe-MOF structure on the surface, carrying out high-temperature phosphorization, calcining in Ar atmosphere, and finally neutralizing with g-C3N4Stirring, heating and evaporating to dryness under the condition of taking methanol as a solvent to obtain CoP/FeP/g-C3N4A heterostructure. The CoP/FeP/g-C3N4Has good photocatalytic performance and is relatively pureCoP, CoP/FeP/g-C of3N4The hydrogen production was 2 times higher than that of CoP.
Description
Technical Field
The invention relates to a modified g-C for photocatalytic hydrogen production3N4A preparation method of a catalyst belongs to the field of material chemistry.
Background
The preparation of hydrogen by using sunlight to irradiate a photocatalyst/water system is the most important problem for relieving energy crisis and global environmental pollutionA promising approach. One of the key challenges in applying photocatalysis to generate hydrogen is to develop catalysts that can efficiently collect visible light and separate photogenerated charges. g-C as a graphite analogue in all available photocatalysts3N4With its flexible layered structure, relatively narrow band gap, reasonable production cost and excellent durability are receiving much attention. However, due to its low visible light absorption, limited active sites and high electron-hole recombination rate, g-C3N4The hydrogen evolution activity of (a) is limited. For this purpose, for example, dye sensitization, construction based on g-C with other semiconductors has been developed3N4And co-catalyst modification to address these limitations. Furthermore, in view of graphitic carbon and g-C3N4Show the same sp between2Bonded pi structure, g-C has been developed3N4Coupling with graphitic carbon to build complexes to increase g-C3N4The charge separation efficiency of (1).
Based on some existing theoretical foundations, a simple method is provided for synthesizing CoP/FeP/g-C3N4The composite photocatalyst is used for enhancing the photocatalytic hydrogen production effect.
Disclosure of Invention
The invention provides a modified g-C for photocatalytic hydrogen production3N4Process for the preparation of the catalyst, the modification g-C3N4The catalyst is CoP/FeP/g-C3N4And (3) compounding a catalyst. The preparation method comprises the steps of firstly synthesizing a ZIF-67 cube and taking the ZIF-67 cube as a precursor, growing a layer of Fe-MOF structure on the surface of the ZIF-67 cube, then placing the ZIF and sodium hypophosphite into a tubular furnace, carrying out phosphorization and calcination in Ar atmosphere to obtain the cobalt-iron bimetal phosphide, and applying the material to photocatalysis. A bilayer structure is formed by growing Fe-MOF on the surface of ZIF-67. CoP taking ZIF-67 as a precursor is combined with carbon nitride as a cocatalyst, so that the separation of photo-generated electron hole pairs is remarkably improved, and the photocatalytic activity of the catalyst is improved; CoP/FeP/g-C obtained by combining hexahedral structure with synergistic effect of second metal Fe3N4To make it photo-catalytically produceThe hydrogen performance is further improved
The invention provides a modified g-C for photocatalytic hydrogen production3N4The preparation method of the catalyst specifically comprises the following steps:
(1) preparation of ZIF-67 cube
Dissolving a proper amount of cobalt nitrate hexahydrate and hexadecyl trimethyl ammonium bromide in methanol to mark as solution A, dissolving a proper amount of 2-methylimidazole in the methanol to mark as solution B, wherein the volume of the solution A is equal to that of the methanol in the solution B; and then pouring the solution B into the solution A, continuously stirring for 15min, standing the mixed solution for 24h, performing centrifugal separation, collecting a sample, washing the sample with methanol and ethanol for three times respectively, and drying the sample in an oven at 60 ℃ to obtain the ZIF-67 cube.
(2) Synthesis of ZIF-67@ Fe-MOF Material
Putting the ZIF-67 cube prepared in the step (1) into ethanol, performing ultrasonic treatment for 10min, adding cobalt nitrate hexahydrate into the mixed solution, and continuing performing ultrasonic treatment for 10min to mark the mixed solution as a C solution; dissolving a proper amount of potassium ferricyanide in a mixed solution of methanol and water, marking the solution as a solution D, quickly pouring the solution D into the solution C, continuously stirring for 2 hours, centrifugally separating, collecting a sample, washing the sample with methanol for three times, and drying the sample in an oven at the temperature of 60 ℃ to obtain ZIF-67@ Fe-MOF.
(3) Preparation of CoP/FeP Compounds
Respectively placing the ZIF-67@ Fe-MOF sample prepared in the step (2) and sodium hypophosphite at two ends of a porcelain boat, placing the porcelain boat in a tube furnace, placing one end of the porcelain boat, where the sodium hypophosphite is placed, at an air inlet, introducing Ar, calcining in the atmosphere of Ar, and obtaining a CoP/FeP compound after the reaction is finished.
(4) Preparation of CoP/FeP/g-C3N4Catalyst and process for preparing same
Mixing the CoP/FeP compound prepared in the step (3) with g-C3N4Mixing, placing in methanol solution, performing ultrasonic treatment for 15min, and stirring at 40 deg.C until the solution is completely volatilized to obtain CoP/FeP/g-C3N4Catalysts, i.e. modified g-C's described for photocatalytic hydrogen production3N4A catalyst.
Further, in the step (1), in the solution A, the mass-to-volume ratio of the cobalt nitrate hexahydrate to the methanol is 7.25g/L, and the mass-to-volume ratio of the hexadecyl trimethyl ammonium bromide to the methanol is 5 g/L; in the solution B, the mass-volume ratio of the 2-methylimidazole to the methanol is 8.2g/L,
further, in the step (1), the speed of magnetic stirring is 400 r/min.
In the step (2), in the solution C, the mass-to-volume ratio of the ZIF-67 cubes to the ethanol is 1g/L, the mass-to-volume ratio of the cobalt nitrate hexahydrate to the ethanol is 7.45g/L, and in the solution D, the mass-to-volume ratio of the potassium ferricyanide to the water is 8 g/L.
Further, the mass ratio of the ZIF-67 cube to the potassium ferricyanide is 1: 2.
further, in the step (3), the mass ratio of the ZIF-67@ Fe-MOF sample to the sodium hypophosphite is 1: 10.
Further, in the step (3), the calcination temperature is 300-400 ℃ in the Ar atmosphere, the calcination time is 2h, and the heating rate is 2 ℃/min.
Further, in the step (4), CoP/FeP and g-C3N4The mass ratio of (1): 50-100 ℃ and 40 ℃.
Further, in the steps (1) to (3), the centrifugal speed is 8000r/min and the time is 5min during centrifugal separation.
Further, in the steps (1) to (3), the rotation speed of stirring is 400 r/min.
Compared with the prior art, the invention has the following beneficial effects:
CoP taking ZIF-67 as a precursor is combined with carbon nitride as a cocatalyst, so that the separation of photo-generated electron hole pairs is remarkably improved, and the photocatalytic activity is improved; CoP/FeP/g-C obtained by combining hexahedral structure with synergistic effect of second metal Fe3N4The photocatalytic hydrogen production performance is further improved. In addition, the transition metal phosphide is used as a cocatalyst instead of noble metal, so that the cost is greatly reduced, and the resources are saved. Thus, the work has been to develop non-noble metal promotersThe problem of low transmission efficiency of a photon-generated carrier of carbon nitride is solved, and light absorption and utilization rate are further improved, so that the photocatalyst with higher photocatalytic performance is obtained, and the method has great significance.
Drawings
FIG. 1 is a scanning electron micrograph of the ZIF-67@ Fe-MOF material of example 1.
FIG. 2 is a SEM photograph of CoP/FeP after phosphating in example 1.
FIG. 3 is CoP/FeP/g-C prepared in example 13N4The obtained photocatalytic hydrogen production performance diagram is obtained by dispersing the catalyst in triethanolamine solution (10 vol%) and irradiating the solution for 4 hours by a 300W xenon lamp (AM 1.5).
The specific implementation mode is as follows:
the invention is further described with reference to the drawings and the detailed description.
Example 1:
(1) preparation of ZIF-67 cube
0.145g of cobalt nitrate hexahydrate and 0.1g of cetyltrimethylammonium bromide were dissolved in 20mL of methanol and designated A solution, and 0.164g of 2-methylimidazole was dissolved in 20mL of methanol and designated B solution. Then, the solution B is poured into the solution A to be stirred for 15min, and then the solution is kept stand for 24 h. After standing, performing centrifugal separation, collecting a sample, washing the sample with methanol and ethanol for three times respectively, and drying the sample in a drying oven at the temperature of 60 ℃ to obtain a ZIF-67 cube;
(2) synthesis of ZIF-67@ Fe-MOF Material
Putting 40mg of the ZIF-67 cube prepared in the step (1) into 40mL of ethanol, carrying out ultrasonic treatment for 10min, then adding 0.298g of cobalt nitrate hexahydrate into the solution, continuing ultrasonic treatment for 10min, marking as a solution C, dissolving 80mg of potassium ferricyanide into a mixed solution of 30mL of methanol and 10mL of water, marking as a solution D, quickly pouring the solution D into the solution C, continuously stirring for 2h, carrying out centrifugal separation, collecting a sample, washing with methanol for three times, and drying in an oven at 60 ℃ to obtain ZIF-67@ Fe-MOF;
(3) preparation of CoP/FeP Compounds
And (3) respectively placing 30mg of the ZIF-67@ Fe-MOF sample prepared in the step (2) and 300mg of sodium hypophosphite at two ends of a porcelain boat, placing the porcelain boat in a tube furnace, placing the sodium hypophosphite at an air inlet, and calcining in Ar atmosphere at the temperature of 350 ℃ for 2h at the temperature rise rate of 2 ℃/min during calcination to obtain the CoP/FeP phosphide after the reaction is finished.
(4) Preparation of CoP/FeP/g-C3N4
Mixing the CoP/FeP prepared in the step (3) with g-C3N4Adding the mixture into a methanol solution according to the mass ratio of 1:50, performing ultrasonic treatment for 15min, and stirring on a stirring table at 40 ℃ until the solution is completely volatilized to finally obtain CoP/FeP/g-C3N4A compound is provided.
Example 2:
(1) preparation of ZIF-67 cube
0.145g of cobalt nitrate hexahydrate and 0.1g of cetyltrimethylammonium bromide were dissolved in 20mL of methanol and designated A solution, and 0.164g of 2-methylimidazole was dissolved in 20mL of methanol and designated B solution. Then, the solution B is poured into the solution A to be stirred for 15min, and then the solution is kept stand for 24 h. After standing, performing centrifugal separation, collecting a sample, washing the sample with methanol and ethanol for three times respectively, and drying the sample in a drying oven at the temperature of 60 ℃ to obtain a ZIF-67 cube;
(2) synthesis of ZIF-67@ Fe-MOF Material
Putting 40mg of the ZIF-67 cube prepared in the step (1) into 40mL of ethanol, carrying out ultrasonic treatment for 10min, then adding 0.298g of cobalt nitrate hexahydrate into the solution, continuing ultrasonic treatment for 10min, marking as a solution C, dissolving 80mg of potassium ferricyanide into a mixed solution of 30mL of methanol and 10mL of water, marking as a solution D, quickly pouring the solution D into the solution C, continuously stirring for 2h, carrying out centrifugal separation, collecting a sample, washing with methanol for three times, and drying in an oven at 60 ℃ to obtain ZIF-67@ Fe-MOF;
(3) preparation of CoP/FeP Compounds
Respectively placing 30mg of the ZIF-67@ Fe-MOF sample prepared in the step (2) and 300mg of sodium hypophosphite at two ends of a porcelain boat, placing the porcelain boat in a tube furnace, placing the sodium hypophosphite in an air inlet, and calcining in Ar atmosphere at the temperature of 300 ℃ for 2h at the temperature rise rate of 2 ℃/min during calcination, thus obtaining the CoP/FeP phosphide after the reaction is finished.
(4) Preparation of CoP/FeP/g-C3N4
Mixing the CoP/FeP prepared in the step (3) with g-C3N4Adding the mixture into a methanol solution according to the mass ratio of 1:100, performing ultrasonic treatment for 15min, and stirring on a stirring table at 40 ℃ until the solution is completely volatilized, thereby obtaining CoP/FeP/g-C3N4A compound is provided.
Example 3:
(1) preparation of ZIF-67 cube
0.145g of cobalt nitrate hexahydrate and 0.1g of cetyltrimethylammonium bromide were dissolved in 20mL of methanol and designated A solution, and 0.164g of 2-methylimidazole was dissolved in 20mL of methanol and designated B solution. Then, the solution B is poured into the solution A to be stirred for 15min, and then the solution is kept stand for 24 h. After standing, performing centrifugal separation, collecting a sample, washing the sample with methanol and ethanol for three times respectively, and drying the sample in a drying oven at the temperature of 60 ℃ to obtain a ZIF-67 cube;
(2) synthesis of ZIF-67@ Fe-MOF Material
Putting 40mg of the ZIF-67 cube prepared in the step (1) into 40mL of ethanol, carrying out ultrasonic treatment for 10min, then adding 0.298g of cobalt nitrate hexahydrate into the solution, continuing ultrasonic treatment for 10min, marking as a solution C, dissolving 80mg of potassium ferricyanide into a mixed solution of 30mL of methanol and 10mL of water, marking as a solution D, quickly pouring the solution D into the solution C, continuously stirring for 2h, carrying out centrifugal separation, collecting a sample, washing with methanol for three times, and drying in an oven at 60 ℃ to obtain ZIF-67@ Fe-MOF;
(3) preparation of CoP/FeP Compounds
Respectively placing 30mg of the ZIF-67@ Fe-MOF sample prepared in the step (2) and 300mg of sodium hypophosphite at two ends of a porcelain boat, placing the porcelain boat in a tube furnace, placing the sodium hypophosphite in an air inlet, and calcining in Ar atmosphere at the temperature of 400 ℃ for 2h at the temperature rise rate of 2 ℃/min during calcination, thus obtaining the CoP/FeP phosphide after the reaction is finished.
(4) Preparation of CoP/FeP/g-C3N4
Mixing the CoP/FeP prepared in the step (3) with g-C3N4Adding the mixture into a methanol solution according to the mass ratio of 1:50, performing ultrasonic treatment for 15min, and stirring on a stirring table at 40 ℃ until the solution is completely volatilized, thereby obtaining CoP/FeP/g-C3N4Compound (I)
The above-mentioned method for preparing the negative electrode material for sodium ion battery, wherein the raw materials are all purchased from the group consisting of Aladdin reagent Co., Ltd and Michelin reagent Co., Ltd, and the equipment and process used are well known to those skilled in the art.
The invention is not the best known technology.
Claims (10)
1. Modified g-C for photocatalytic hydrogen production3N4The preparation method of the catalyst specifically comprises the following steps:
(1) preparation of ZIF-67 cube
Dissolving a proper amount of cobalt nitrate hexahydrate and hexadecyl trimethyl ammonium bromide in methanol to mark as solution A, dissolving a proper amount of 2-methylimidazole in the methanol to mark as solution B, wherein the volume of the solution A is equal to that of the methanol in the solution B; then pouring the solution B into the solution A, continuously stirring for 15min, standing the mixed solution for 24h, performing centrifugal separation, collecting a sample, washing the sample with methanol and ethanol for three times respectively, and drying the sample in a drying oven at 60 ℃ to obtain a ZIF-67 cube;
(2) synthesis of ZIF-67@ Fe-MOF Material
Putting the ZIF-67 cube prepared in the step (1) into ethanol, performing ultrasonic treatment for 10min, adding cobalt nitrate hexahydrate into the mixed solution, and continuing performing ultrasonic treatment for 10min to mark the mixed solution as a C solution; dissolving a proper amount of potassium ferricyanide in a mixed solution of methanol and water, marking the solution as a solution D, quickly pouring the solution D into the solution C, continuously stirring for 2 hours, performing centrifugal separation, collecting a sample, washing the sample with methanol for three times, and drying the sample in a drying oven at the temperature of 60 ℃ to obtain a ZIF-67@ Fe-MOF material;
(3) preparation of CoP/FeP Compounds
Respectively placing the ZIF-67@ Fe-MOF sample prepared in the step (2) and sodium hypophosphite at two ends of a porcelain boat, placing the porcelain boat in a tube furnace, placing one end of the porcelain boat where the sodium hypophosphite is placed at an air inlet, introducing Ar, calcining in the atmosphere of Ar, and obtaining a CoP/FeP compound after the reaction is finished;
(4) preparation of CoP/FeP/g-C3N4Catalyst and process for preparing same
Mixing the CoP/FeP compound prepared in the step (3) with g-C3N4Mixing, placing in methanol solution, performing ultrasonic treatment for 15min, and stirring at 40 deg.C until the solution is completely volatilized to obtain CoP/FeP/g-C3N4Catalysts, i.e. modified g-C's described for photocatalytic hydrogen production3N4A catalyst.
2. The preparation method according to claim 1, wherein in the solution A in the step (1), the mass-to-volume ratio of the cobalt nitrate hexahydrate to the methanol is 7.25g/L, and the mass-to-volume ratio of the cetyltrimethylammonium bromide to the methanol is 5 g/L; in the solution B, the mass-to-volume ratio of the 2-methylimidazole to the methanol is 8.2 g/L.
3. The method according to claim 1, wherein in the step (1), the magnetic stirring speed is 400 r/min.
4. The preparation method according to claim 1, wherein in the step (2), the mass-to-volume ratio of the ZIF-67 cubes to the ethanol in the solution C is 1g/L, the mass-to-volume ratio of the cobalt nitrate hexahydrate to the ethanol is 7.45g/L, and the mass-to-volume ratio of the potassium ferricyanide to the water in the solution D is 8 g/L.
5. The method according to claim 4, wherein the mass ratio of the ZIF-67 cube to the potassium ferricyanide is 1: 2.
6. the method according to claim 1, wherein in the step (3), the mass ratio of the sample of ZIF-67@ Fe-MOF to the sodium hypophosphite is 1: 10.
7. The preparation method according to claim 1, wherein in the step (3), the calcination temperature in Ar atmosphere is 300-400 ℃, the calcination time is 2h, and the temperature rise rate is 2 ℃/min.
8. The process according to claim 1, wherein in the step (4), CoP/FeP and g-C are used3N4The mass ratio of (A) to (B) is 1: 50-100.
9. The method according to claim 1, wherein the centrifugation is carried out at 8000r/min for 5min in the steps (1) to (3).
10. The production method according to claim 1, wherein the rotation speed of the stirring in the steps (1) to (3) is 400 r/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659454A (en) * | 2020-07-29 | 2020-09-15 | 重庆工商大学 | g-C3N4Preparation method and application of/Ni @ C/NiP photocatalyst |
| CN111943155A (en) * | 2020-07-08 | 2020-11-17 | 江西师范大学 | Preparation method of composite cobalt phosphide nano polyhedron with yolk shell structure |
| CN112371189A (en) * | 2020-11-11 | 2021-02-19 | 浙江工业大学 | Hydroxide-coated ZIF (zinc-oxygen-doped organic framework) MOFs (metal-organic frameworks) heterogeneous catalyst and preparation and application thereof |
| CN114522712A (en) * | 2022-02-22 | 2022-05-24 | 嘉兴学院 | Amphiphilic CoP/g-C for degrading micro-plastic and synergistically producing hydrogen3N4Material and method for producing same |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150259810A1 (en) * | 2014-03-17 | 2015-09-17 | California Institute Of Technology | Hydrogen evolution reaction catalysis |
| CN105720278A (en) * | 2016-03-31 | 2016-06-29 | 华中科技大学 | High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof |
| CN105895886A (en) * | 2016-06-21 | 2016-08-24 | 中南大学 | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof |
| CN106311294A (en) * | 2016-07-26 | 2017-01-11 | 北京工业大学 | Method for preparing zinc phosphide/cobalt phosphide heterojunction photocatalyst based on MOFs template |
| CN107126971A (en) * | 2017-07-09 | 2017-09-05 | 华东理工大学 | A kind of preparation and application of compound CoP/g C3N4 photochemical catalysts |
| CN107552083A (en) * | 2017-10-11 | 2018-01-09 | 肇庆市华师大光电产业研究院 | A kind of FeP/C3N4Composite photo-catalyst and its preparation method and application |
| CN107955950A (en) * | 2017-11-17 | 2018-04-24 | 中国科学院深圳先进技术研究院 | A kind of preparation method of catalyst material |
| CN109107597A (en) * | 2018-08-31 | 2019-01-01 | 华南农业大学 | A kind of transition metal phosphide/g-C3N4Composite material and preparation method and application |
| EP3424594A1 (en) * | 2017-07-06 | 2019-01-09 | Ecole Polytechnique Federale De Lausanne (Epfl) | Photocatalytic system comprising a titanium-based mof |
| CN109433240A (en) * | 2018-10-26 | 2019-03-08 | 济南大学 | A kind of nitrogen-doped carbon nano-array load iron phosphide/phosphatization cobalt preparation method |
| CN110745788A (en) * | 2019-10-15 | 2020-02-04 | 肇庆市华师大光电产业研究院 | Preparation method of sodium ion battery cathode material of molybdenum-cobalt bimetallic selenide |
| CN110743603A (en) * | 2019-11-21 | 2020-02-04 | 江苏索普（集团）有限公司 | Cobalt-iron bimetallic nitride composite electrocatalyst and preparation method and application thereof |
-
2020
- 2020-02-20 CN CN202010103471.0A patent/CN111250137A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150259810A1 (en) * | 2014-03-17 | 2015-09-17 | California Institute Of Technology | Hydrogen evolution reaction catalysis |
| CN105720278A (en) * | 2016-03-31 | 2016-06-29 | 华中科技大学 | High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof |
| CN105895886A (en) * | 2016-06-21 | 2016-08-24 | 中南大学 | Transition metal phosphide/porous carbon anode composite material for sodium-ion battery and preparation method thereof |
| CN106311294A (en) * | 2016-07-26 | 2017-01-11 | 北京工业大学 | Method for preparing zinc phosphide/cobalt phosphide heterojunction photocatalyst based on MOFs template |
| EP3424594A1 (en) * | 2017-07-06 | 2019-01-09 | Ecole Polytechnique Federale De Lausanne (Epfl) | Photocatalytic system comprising a titanium-based mof |
| CN107126971A (en) * | 2017-07-09 | 2017-09-05 | 华东理工大学 | A kind of preparation and application of compound CoP/g C3N4 photochemical catalysts |
| CN107552083A (en) * | 2017-10-11 | 2018-01-09 | 肇庆市华师大光电产业研究院 | A kind of FeP/C3N4Composite photo-catalyst and its preparation method and application |
| CN107955950A (en) * | 2017-11-17 | 2018-04-24 | 中国科学院深圳先进技术研究院 | A kind of preparation method of catalyst material |
| CN109107597A (en) * | 2018-08-31 | 2019-01-01 | 华南农业大学 | A kind of transition metal phosphide/g-C3N4Composite material and preparation method and application |
| CN109433240A (en) * | 2018-10-26 | 2019-03-08 | 济南大学 | A kind of nitrogen-doped carbon nano-array load iron phosphide/phosphatization cobalt preparation method |
| CN110745788A (en) * | 2019-10-15 | 2020-02-04 | 肇庆市华师大光电产业研究院 | Preparation method of sodium ion battery cathode material of molybdenum-cobalt bimetallic selenide |
| CN110743603A (en) * | 2019-11-21 | 2020-02-04 | 江苏索普（集团）有限公司 | Cobalt-iron bimetallic nitride composite electrocatalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| ENLAI HU ET AL.: ""A Room-Temperature Postsynthetic Ligand Exchange Strategy to Construct Mesoporous Fe-Doped CoP Hollow Triangle Plate Arrays for Efficient Electrocatalytic Water Splitting"", 《SMALL》 * |
| XIAO-JUN SUN ET AL.: ""ZIF-derived CoP as a cocatalyst for enhanced photocatalytic H2 production activity of g-C3N4"", 《SUSTAINABLE ENERGY & FUELS》 * |
| 杨玉美 等: ""ZIF-67衍生的磷化钴/碳复合材料的制备及电化学析氢性能研究"", 《河南省化学会2018年学术年会摘要集》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111943155A (en) * | 2020-07-08 | 2020-11-17 | 江西师范大学 | Preparation method of composite cobalt phosphide nano polyhedron with yolk shell structure |
| CN111659454A (en) * | 2020-07-29 | 2020-09-15 | 重庆工商大学 | g-C3N4Preparation method and application of/Ni @ C/NiP photocatalyst |
| CN111659454B (en) * | 2020-07-29 | 2022-12-23 | 重庆工商大学 | g-C 3 N 4 Preparation method and application of/Ni @ C/NiP photocatalyst |
| CN112371189A (en) * | 2020-11-11 | 2021-02-19 | 浙江工业大学 | Hydroxide-coated ZIF (zinc-oxygen-doped organic framework) MOFs (metal-organic frameworks) heterogeneous catalyst and preparation and application thereof |
| CN114522712A (en) * | 2022-02-22 | 2022-05-24 | 嘉兴学院 | Amphiphilic CoP/g-C for degrading micro-plastic and synergistically producing hydrogen3N4Material and method for producing same |
| CN114522712B (en) * | 2022-02-22 | 2023-12-01 | 嘉兴学院 | Amphiphilic CoP/g-C for synergistic hydrogen production of degraded microplastic 3 N 4 Material and preparation method thereof |
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