CN110721747A - Metal organic framework photocatalytic hydrogen production composite material and preparation method thereof - Google Patents
Metal organic framework photocatalytic hydrogen production composite material and preparation method thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002073 nanorod Substances 0.000 claims abstract description 48
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 40
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013110 organic ligand Substances 0.000 claims abstract description 17
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910000370 mercury sulfate Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 40
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- 239000012153 distilled water Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012265 solid product Substances 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 13
- -1 (p-carboxyphenyl) amino Chemical group 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 229940079593 drug Drugs 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000005855 radiation Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 25
- 239000011941 photocatalyst Substances 0.000 description 8
- 238000005381 potential energy Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229940074994 mercuric sulfate Drugs 0.000 description 2
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003786 synthesis reaction 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/28—Mercury
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- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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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
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of photocatalytic hydrogen production materials, and discloses a metal organic framework photocatalytic hydrogen production composite material and a preparation method thereof, wherein the metal organic framework photocatalytic hydrogen production composite material comprises the following formula raw materials: titanium dioxide nanorods, mercury sulfate and organic ligands. The metal organic framework photocatalytic hydrogen production composite material and the preparation method thereof, the metal organic framework Hg3(TATAB)2Is a stable regular octahedron conical structure, has a large number of regular pore channel structures and huge specific surface area, so that the catalyst has high-density and uniformly-dispersed catalytic active sites, promotes the transmission and migration of reaction substrates and products, improves the separation efficiency of photoproduction electrons and holes, accelerates the catalytic reaction, and Hg is a positive octahedron conical structure3(TATAB)2Uniformly dispersed on the surface of the titanium dioxide nano rod, thereby avoiding Hg3(TATAB)2Easy agglomeration into large particles in the reaction process and evenly distributed Hg3(TATAB)2Active sites in direct contact with light radiation and water molecules are increased, so that the titanium dioxide nano-rods and Hg are attached to the active sites3(TATAB)2Can efficiently transfer electrons.
Description
Technical Field
The invention relates to the technical field of photocatalytic hydrogen production materials, in particular to a metal organic framework photocatalytic hydrogen production composite material and a preparation method thereof.
Background
TiO2The single crystal electrode photocatalytically decomposes water to generate hydrogen, so that the hydrogen production by directly decomposing water by solar energy becomes possible, and in the research of the hydrogen production by photocatalytically decomposing water in recent years, great progress is made in the aspects of synthesis, modification and the like of photocatalysts, and the photocatalytically reacting to decompose neutral water into H2And O2The reaction converts light energy into chemical energy and is based on the principle that light is radiated onto semiconductor and when the energy of the light radiation is greater than the forbidden bandwidth of the semiconductor, the electricity in the semiconductor is generatedThe proton changes to excited state, transits from valence band to conduction band, and the water is reduced to H2While holes remain in the valence band, which separates electrons and holes and oxidizes water to produce oxygen.
The existing catalyst for producing hydrogen by photolysis of water mainly comprises tantalate KTaO3、A2SrTa2O7·nH2O, niobate Ba5LaTi2Nb3O18Titanate, Au loaded K2La2Ti3O10The metal organic framework is a crystalline porous organic-inorganic hybrid material with a periodic network structure formed by mutually connecting an inorganic metal center and a bridged organic ligand through self assembly, and high-activity electrons and holes can be generated in the process of transferring charges to the metal center by the organic ligand under illumination, so that the metal organic framework has photocatalytic activity, but the compound is easy to agglomerate and has poor dispersibility in the catalytic process of the existing metal organic framework photocatalyst, the contact of an active site with light radiation and water molecules is insufficient, the catalytic effect of the material is reduced, the generated photo-generated electrons and holes are easy to compound, the photocatalytic activity is low, the efficiency and the performance of photocatalytic hydrogen production are reduced, and meanwhile, the structure and the chemical stability of most of the existing metal organic framework photocatalysts are poor, the practicability and durability of the photocatalyst in the practical application process are reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a metal organic framework photocatalytic hydrogen production composite material and a preparation method thereof, which solve the problems that a compound is easy to agglomerate, the dispersibility is poor, and active sites are not in sufficient contact with light radiation and water molecules in the catalytic process of the existing metal organic framework photocatalyst, and solve the problems that the structure and the chemical stability of the metal organic framework photocatalyst are poor, and the practicability and the durability in the practical application process are poor.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the metal organic framework photocatalytic hydrogen production composite material comprises the following formula raw materials, 26-42 parts of titanium dioxide nanorods, 40-52 parts of mercury sulfate and 18-22 parts of organic ligands in parts by weight, and the preparation method comprises the following experimental medicines: distilled water, ethylene glycol, absolute ethyl alcohol, hydrofluoric acid solution, isopropyl titanate, hexadecyl trimethyl ammonium bromide and ethyl acetate.
Preferably, the mercury sulfate, distilled water, ethylene glycol, absolute ethyl alcohol, ethyl acetate, isopropyl titanate and hexadecyl trimethyl ammonium bromide are all chemically pure.
Preferably, the mass fraction of the hydrofluoric acid solution is more than or equal to 45%.
Preferably, the preparation method of the titanium dioxide nanorod comprises the following steps: adding 5-7 parts of hydrofluoric acid solution into a reaction bottle, slowly adding 25-32 parts of isopropyl titanate, stirring at constant speed for 30-50min, slowly adding 10-15 parts of distilled water, heating the three-necked flask in a constant temperature oil bath to 60-65 deg.C, sequentially adding 46-60 parts of hexadecyl trimethyl ammonium bromide and ethylene glycol, controlling the solution mass fraction to be 10-15%, stirring at constant speed until the hexadecyl trimethyl ammonium bromide is completely dissolved, slowly dripping the solution in the reaction flask into the three-necked flask, and raising the temperature of the oil bath to 170-180 ℃ for reaction for 20-25 h, filtering the material after the reaction is finished to remove the solvent to obtain a solid product, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and placing the solid product in an oven for heating and drying to obtain the titanium dioxide nano rod.
Preferably, the organic ligand is 2,4, 6-tris [ (p-carboxyphenyl) amino group]-1,3, 5-triazine with the formula C24H18N6O6Structural formula is。
Preferably, the preparation method of the metal organic framework photocatalytic hydrogen production composite material is as follows:
(1) preparation of metal organic framework Hg3(TATAB)2: adding 200 materials into a high-pressure hydrothermal automatic reaction kettle300 mL of distilled water, then weighing 40-52 parts of mercury sulfate, fully stirring uniformly, adding 400-700 mL of dimethyl sulfoxide and 18-22 parts of organic ligand 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine, setting a high-pressure hydrothermal automatic reaction kettle at 170 ℃, uniformly stirring and reacting for 25-30 h, cooling the reaction kettle to room temperature after the reaction is finished, filtering the material to remove the solvent, washing the material with appropriate amount of distilled water and ethyl acetate in turn, and drying in an oven to obtain the metal organic framework Hg3(TATAB)2。
(2) Preparation of Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material: adding 1000mL of anhydrous ethanol of 600-3(TATAB)2And 26-42 parts of titanium dioxide nano-rods, placing the beaker in a high-pressure hydrothermal automatic reaction kettle, raising the temperature to 120-130 ℃, stirring at constant speed for activation reaction for 3-6h, then transferring the materials in the reaction kettle into an ultrasonic treatment instrument, heating to 50-55 ℃ at the ultrasonic frequency of 25-28 KHz, and performing ultrasonic dispersion for 4-6 h to ensure that Hg is dispersed for 4-6 h3(TATAB)2Completely loaded on the surface and the inner wall of the titanium dioxide nano rod to obtain Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
1. the metal organic framework Hg is used for preparing the photocatalytic hydrogen production composite material3(TATAB)2As the main matrix material of the photocatalyst, the regular octahedral conical structure has better chemical stability, Hg3(TATAB)2The structure has a large number of regular pore channel structures and huge specific surface area, so that the structure has catalytic active sites with high density and uniform dispersion, and the high pore channel structure improves the accessibility of the accessibility center of the catalytic active center, promotes the transmission and migration of reaction substrates and products, reduces the recombination of photo-generated electrons and holes, improves the separation efficiency of the photo-generated electrons and the holes, and accelerates the catalytic activityThe photocatalytic activity and the photo-hydrogen production efficiency of the material are improved by the chemical reaction.
2. The photocatalytic hydrogen production composite material with the metal organic framework comprises titanium dioxide nanorods, the titanium dioxide nanorods are activated by a hydrothermal method, and the metal organic framework Hg is activated by an ultrasonic dispersion method3(TATAB)2Uniformly dispersed on the surface of the titanium dioxide nano rod, thereby avoiding Hg3(TATAB)2Easy agglomeration into large particles in the reaction process and evenly distributed Hg3(TATAB)2Increases the active sites of the titanium dioxide nano-rod in direct contact with light radiation and water molecules, and leads the titanium dioxide nano-rod and Hg to be in contact with each other3(TATAB)2The composite material has an oxidation potential energy gap of 1.62 eV, a reduction potential energy gap of 1.57 eV, an oxidation potential energy level of 0.46 eV, a reduction potential energy level of-1.16 eV, and a specific H ratio+The energy level value of the reduced hydrogen is more negative, and the photocatalytic hydrogen production efficiency reaches 35-42 mu mol/(g.h), so the composite material has stronger photocatalytic hydrogen production performance.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: the metal organic framework photocatalytic hydrogen production composite material comprises the following formula raw materials, 26-42 parts of titanium dioxide nanorods, 40-52 parts of mercury sulfate and 18-22 parts of organic ligands in parts by weight, and the preparation method comprises the following experimental medicines: distilled water, glycol, absolute ethyl alcohol, hydrofluoric acid solution, isopropyl titanate, hexadecyl trimethyl ammonium bromide, ethyl acetate and mercury sulfate, which are all chemically pure, wherein the mass fraction of the hydrofluoric acid solution is more than or equal to 45 percent, and the organic ligand is 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine with the formula C24H18N6O6Structural formula is。
The preparation method of the titanium dioxide nano rod comprises the following steps: adding 5-7 parts of hydrofluoric acid solution into a reaction bottle, slowly adding 25-32 parts of isopropyl titanate, stirring at constant speed for 30-50min, slowly adding 10-15 parts of distilled water, heating the three-necked flask in a constant temperature oil bath to 60-65 deg.C, sequentially adding 46-60 parts of hexadecyl trimethyl ammonium bromide and ethylene glycol, controlling the solution mass fraction to be 10-15%, stirring at constant speed until the hexadecyl trimethyl ammonium bromide is completely dissolved, slowly dripping the solution in the reaction flask into the three-necked flask, and raising the temperature of the oil bath to 170-180 ℃ for reaction for 20-25 h, filtering the material after the reaction is finished to remove the solvent to obtain a solid product, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and placing the solid product in an oven for heating and drying to obtain the titanium dioxide nano rod.
The preparation method of the metal organic framework photocatalytic hydrogen production composite material comprises the following steps:
(1) preparation of metal organic framework Hg3(TATAB)2: adding 200-300 mL of distilled water into a high-pressure hydrothermal automatic reaction kettle, weighing 40-52 parts of mercury sulfate, fully stirring uniformly, adding 400-700 mL of dimethyl sulfoxide and 18-22 parts of organic ligand 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine, setting a high-pressure hydrothermal automatic reaction kettle at 170 ℃, uniformly stirring and reacting for 25-30 h, cooling the reaction kettle to room temperature after the reaction is finished, filtering the material to remove the solvent, washing the material with appropriate amount of distilled water and ethyl acetate in turn, and drying in an oven to obtain the metal organic framework Hg3(TATAB)2。
(2) Preparation of Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material: adding 1000mL of anhydrous ethanol of 600-3(TATAB)2And 26-42 parts of titanium dioxide nano-rods, placing the beaker in a high-pressure hydrothermal automatic reaction kettle, raising the temperature to 120-130 ℃, stirring at constant speed for activation reaction for 3-6h, then transferring the materials in the reaction kettle into an ultrasonic treatment instrument, heating to 50-55 ℃ at the ultrasonic frequency of 25-28 KHz, and performing ultrasonic dispersion for 4-6 h to ensure that Hg is dispersed for 4-6 h3(TATAB)2Completely loaded on the surface and the inner wall of the titanium dioxide nano rod to obtain Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material.
Example 1:
(1) preparing a titanium dioxide nanorod: adding 5 parts of hydrofluoric acid solution into a reaction bottle, slowly adding 25 parts of isopropyl titanate, stirring at a constant speed for 30 min, slowly adding 10 parts of distilled water, placing a three-necked bottle into a constant-temperature oil bath kettle, heating to 60 ℃, sequentially adding 60 parts of hexadecyl trimethyl ammonium bromide and ethylene glycol, controlling the mass fraction of the solution to be 10%, stirring at a constant speed until the hexadecyl trimethyl ammonium bromide is completely dissolved, slowly dripping the solution in the reaction bottle into the three-necked bottle, raising the temperature of the oil bath kettle to 170 ℃, reacting for 20 h, filtering the material after the reaction to remove the solvent to obtain a solid product, sequentially washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and heating and drying in an oven to obtain the titanium dioxide nanorod component 1.
(2) Preparation of metal organic framework Hg3(TATAB)2: adding 200 mL of distilled water into a high-pressure hydrothermal automatic reaction kettle, weighing 40 parts of mercuric sulfate, fully stirring uniformly, adding 400 mL of dimethyl sulfoxide and 18 parts of organic ligand 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine, setting a high-pressure hydrothermal automatic reaction kettle at 150 ℃, uniformly stirring for reaction for 25 hours, cooling the reaction kettle to room temperature after the reaction is finished, filtering the material to remove the solvent, washing the material with appropriate amount of distilled water and ethyl acetate in sequence, and drying in an oven to obtain the metal organic framework Hg3(TATAB)2And (3) component 1.
(3) Preparation of Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material: adding 600 mL of absolute ethyl alcohol into a beaker, and adding the metal organic framework Hg prepared in the step (1)3(TATAB)2Placing a beaker into a high-pressure hydrothermal automatic reaction kettle, heating to 120 ℃, uniformly stirring for activation reaction for 3 hours, transferring the materials in the reaction kettle into an ultrasonic treatment instrument, heating to 50 ℃ at the ultrasonic frequency of 25 KHz, and performing ultrasonic dispersion for 4 hours to ensure that Hg is dispersed for 4 hours3(TATAB)2Completely loaded on the surface and the inner wall of the titanium dioxide nano rod to obtain Hg3(TATAB)2-titanium dioxideA nanorod photocatalytic hydrogen production composite material 1.
Example 2:
(1) preparing a titanium dioxide nanorod: adding 5 parts of hydrofluoric acid solution into a reaction bottle, slowly adding 26 parts of isopropyl titanate, stirring at a constant speed for 30 min, slowly adding 11 parts of distilled water, placing a three-necked bottle into a constant-temperature oil bath kettle, heating to 65 ℃, sequentially adding 58 parts of hexadecyl trimethyl ammonium bromide and ethylene glycol, controlling the mass fraction of the solution to be 10%, stirring at a constant speed until the hexadecyl trimethyl ammonium bromide is completely dissolved, slowly dripping the solution in the reaction bottle into the three-necked bottle, raising the temperature of the oil bath kettle to 175 ℃, reacting for 20 h, filtering the material after the reaction to remove the solvent to obtain a solid product, sequentially washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and heating and drying in an oven to obtain the titanium dioxide nanorod component 2.
(2) Preparation of metal organic framework Hg3(TATAB)2: adding 200 mL of distilled water into a high-pressure hydrothermal automatic reaction kettle, weighing 42 parts of mercuric sulfate, fully stirring uniformly, adding 500 mL of dimethyl sulfoxide and 19 parts of organic ligand 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine, setting a high-pressure hydrothermal automatic reaction kettle at 160 ℃, uniformly stirring for reaction for 25 hours, cooling the reaction kettle to room temperature after the reaction is finished, filtering the material to remove the solvent, washing the material with appropriate amount of distilled water and ethyl acetate in sequence, and drying in an oven to obtain the metal organic framework Hg3(TATAB)2And (3) component 2.
(3) Preparation of Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material: adding 800 mL of absolute ethyl alcohol into a beaker, and adding the metal organic framework Hg prepared in the step (1)3(TATAB)2Placing a beaker into a high-pressure hydrothermal automatic reaction kettle, heating to 125 ℃, uniformly stirring for activation reaction for 3 hours, transferring the materials in the reaction kettle into an ultrasonic treatment instrument, heating to 50 ℃ at the ultrasonic frequency of 25 KHz, and performing ultrasonic dispersion for 5 hours to ensure that Hg is dispersed for 5 hours3(TATAB)2Completely loaded on the surface and the inner wall of the titanium dioxide nano rod to obtain Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material 2.
Example 3:
(1) preparing a titanium dioxide nanorod: adding 6 parts of hydrofluoric acid solution into a reaction bottle, slowly adding 28 parts of isopropyl titanate, stirring at a constant speed for 40 min, slowly adding 12 parts of distilled water, placing a three-necked bottle into a constant-temperature oil bath kettle, heating to 65 ℃, sequentially adding 54 parts of hexadecyl trimethyl ammonium bromide and ethylene glycol, controlling the mass fraction of the solution to be 12%, stirring at a constant speed until the hexadecyl trimethyl ammonium bromide is completely dissolved, slowly dripping the solution in the reaction bottle into the three-necked bottle, raising the temperature of the oil bath kettle to 175 ℃, reacting for 20 h, filtering the material after the reaction to remove the solvent to obtain a solid product, sequentially washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and heating and drying in an oven to obtain the titanium dioxide nanorod component 3.
(2) Preparation of metal organic framework Hg3(TATAB)2: adding 250 mL of distilled water into a high-pressure hydrothermal automatic reaction kettle, weighing 47 parts of mercury sulfate, fully stirring uniformly, adding 600 mL of dimethyl sulfoxide and 20 parts of organic ligand 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine, setting a high-pressure hydrothermal automatic reaction kettle at 160 ℃, uniformly stirring for reaction for 28 hours, cooling the reaction kettle to room temperature after the reaction is finished, filtering the material to remove the solvent, washing the material with appropriate amount of distilled water and ethyl acetate in turn, and drying in an oven to obtain the metal organic framework Hg3(TATAB)2And (3) component.
(3) Preparation of Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material: adding 800 mL of absolute ethyl alcohol into a beaker, and adding the metal organic framework Hg prepared in the step (1)3(TATAB)2Placing a beaker into a high-pressure hydrothermal automatic reaction kettle, heating to 125 ℃, uniformly stirring for activation reaction for 5 hours, transferring the materials in the reaction kettle into an ultrasonic treatment instrument, heating to 55 ℃ at the ultrasonic frequency of 25 KHz, and ultrasonically dispersing for 5 hours to ensure that Hg is dispersed for 5 hours3(TATAB)2Complete loading to dioxygenThe surface and the inner wall of the titanium nano rod are transformed to obtain Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material 3.
Example 4:
(1) preparing a titanium dioxide nanorod: adding 6 parts of hydrofluoric acid solution into a reaction bottle, slowly adding 30 parts of isopropyl titanate, stirring at a constant speed for 40 min, slowly adding 14 parts of distilled water, placing a three-necked bottle into a constant-temperature oil bath, heating to 65 ℃, sequentially adding 50 parts of hexadecyl trimethyl ammonium bromide and ethylene glycol, controlling the mass fraction of the solution to be 12%, stirring at a constant speed until the hexadecyl trimethyl ammonium bromide is completely dissolved, slowly dripping the solution in the reaction bottle into the three-necked bottle, raising the temperature of the oil bath to 175 ℃, reacting for 25h, filtering the material after the reaction to remove the solvent to obtain a solid product, sequentially washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and heating and drying in an oven to obtain a titanium dioxide nanorod component 4.
(2) Preparation of metal organic framework Hg3(TATAB)2: adding 300 mL of distilled water into a high-pressure hydrothermal automatic reaction kettle, weighing 49 parts of mercury sulfate, fully stirring uniformly, adding 600 mL of dimethyl sulfoxide and 21 parts of organic ligand 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine, setting a high-pressure hydrothermal automatic reaction kettle at 160 ℃, uniformly stirring for reaction for 30 hours, cooling the reaction kettle to room temperature after the reaction is finished, filtering the material to remove the solvent, washing the material with appropriate amount of distilled water and ethyl acetate in sequence, and drying in an oven to obtain the metal organic framework Hg3(TATAB)2And (4) component.
(3) Preparation of Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material: adding 1000mL of absolute ethyl alcohol into a beaker, and adding the metal organic framework Hg prepared in the step (1)3(TATAB)2Placing a beaker into a high-pressure hydrothermal automatic reaction kettle, heating to 130 ℃, uniformly stirring for activation reaction for 4 hours, transferring the materials in the reaction kettle into an ultrasonic treatment instrument, heating to 55 ℃ at the ultrasonic frequency of 28 KHz, and ultrasonically dispersing for 6 hours to ensure that Hg is dispersed for 6 hours3(TATAB)2Completely loaded on the surface and the inner wall of the titanium dioxide nano rod to obtain Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material 4.
Example 5:
(1) preparing a titanium dioxide nanorod: adding 7 parts of hydrofluoric acid solution into a reaction bottle, slowly adding 32 parts of isopropyl titanate, stirring at a constant speed for 50min, slowly adding 15 parts of distilled water, placing a three-necked bottle into a constant-temperature oil bath kettle, heating to 65 ℃, sequentially adding 46 parts of hexadecyl trimethyl ammonium bromide and ethylene glycol, controlling the mass fraction of the solution to be 15%, stirring at a constant speed until the hexadecyl trimethyl ammonium bromide is completely dissolved, slowly dripping the solution in the reaction bottle into the three-necked bottle, raising the temperature of the oil bath kettle to 180 ℃, reacting for 25h, filtering the material after the reaction to remove the solvent to obtain a solid product, sequentially washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol, and heating and drying in an oven to obtain the titanium dioxide nanorod component 5.
(2) Preparation of metal organic framework Hg3(TATAB)2: adding 300 mL of distilled water into a high-pressure hydrothermal automatic reaction kettle, weighing 52 parts of mercury sulfate, fully stirring uniformly, adding 700 mL of dimethyl sulfoxide and 22 parts of organic ligand 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine, setting a high-pressure hydrothermal automatic reaction kettle at 170 ℃, uniformly stirring for reaction for 30 hours, cooling the reaction kettle to room temperature after the reaction is finished, filtering the material to remove the solvent, washing the material with appropriate amount of distilled water and ethyl acetate in sequence, and drying in an oven to obtain the metal organic framework Hg3(TATAB)2And (5) component.
(3) Preparation of Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material: adding 1000mL of absolute ethyl alcohol into a beaker, and adding the metal organic framework Hg prepared in the step (1)3(TATAB)2Placing a beaker into a high-pressure hydrothermal automatic reaction kettle, heating to 130 ℃, uniformly stirring for carrying out activation reaction for 6 hours, transferring the materials in the reaction kettle into an ultrasonic treatment instrument with the ultrasonic frequency of 28 KHz, and heating until the materials are heated to the temperature of 130 ℃, wherein the titanium dioxide nanorod component 5 is 26 partsUltrasonic dispersing at 55 deg.C for 6 hr to obtain Hg3(TATAB)2Completely loaded on the surface and the inner wall of the titanium dioxide nano rod to obtain Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material 5.
The photocatalytic hydrogen production efficiency of the metal organic framework photocatalytic hydrogen production composite material and the preparation method thereof are tested by the examples 1 to 5, and Hg is used as the metal organic framework3(TATAB)2As the main matrix material of the photocatalyst, the regular octahedral conical structure has better chemical stability, Hg3(TATAB)2The structure has a large number of regular pore channel structures and huge specific surface area, so that the structure has catalytic active sites with high density and uniform dispersion, and the high pore channel structure improves the accessibility of the accessibility center of the catalytic active center, promotes the transmission and migration of reaction substrates and products, reduces the recombination of photo-generated electrons and holes, improves the separation efficiency of the photo-generated electrons and the holes, accelerates the catalytic reaction, and improves the photocatalytic activity and the photo-hydrogen production efficiency of the material.
The photocatalytic hydrogen production composite material with the metal organic framework comprises titanium dioxide nanorods, the titanium dioxide nanorods are activated by a hydrothermal method, and the metal organic framework Hg is activated by an ultrasonic dispersion method3(TATAB)2Uniformly dispersed on the surface of the titanium dioxide nano rod, thereby avoiding Hg3(TATAB)2Easy agglomeration into large particles in the reaction process and evenly distributed Hg3(TATAB)2Increases the active sites of the titanium dioxide nano-rod in direct contact with light radiation and water molecules, and leads the titanium dioxide nano-rod and Hg to be in contact with each other3(TATAB)2The composite material has an oxidation potential energy gap of 1.62 eV, a reduction potential energy gap of 1.57 eV, an oxidation potential energy level of 0.46 eV, a reduction potential energy level of-1.16 eV, and a specific H ratio+The energy level value of the reduced hydrogen is more negative, and the photocatalytic hydrogen production efficiency reaches 35-42 mu mol/(g.h), so the composite material has stronger photocatalytic hydrogen production performance.
Claims (6)
1. The metal organic framework photocatalytic hydrogen production composite material comprises the following formula raw materials in parts by weight, and is characterized in that: 26-42 parts of titanium dioxide nano-rods, 40-52 parts of mercury sulfate and 18-22 parts of organic ligands, and the preparation method comprises the following experimental medicines: distilled water, ethylene glycol, absolute ethyl alcohol, hydrofluoric acid solution, isopropyl titanate, hexadecyl trimethyl ammonium bromide and ethyl acetate.
2. The metal organic framework photocatalytic hydrogen production composite material and the preparation method thereof according to claim 1, wherein the metal organic framework photocatalytic hydrogen production composite material is characterized in that: the mercury sulfate, the distilled water, the glycol, the absolute ethyl alcohol, the ethyl acetate, the isopropyl titanate and the hexadecyl trimethyl ammonium bromide are all chemically pure.
3. The metal organic framework photocatalytic hydrogen production composite material and the preparation method thereof according to claim 1, wherein the metal organic framework photocatalytic hydrogen production composite material is characterized in that: the mass fraction of the hydrofluoric acid solution is more than or equal to 45 percent.
4. The metal organic framework photocatalytic hydrogen production composite material and the preparation method thereof according to claim 1, wherein the metal organic framework photocatalytic hydrogen production composite material is characterized in that: the preparation method of the titanium dioxide nanorod comprises the following steps:
adding 5-7 parts of hydrofluoric acid solution into a reaction bottle, slowly adding 25-32 parts of isopropyl titanate, stirring at constant speed for 30-50min, slowly adding 10-15 parts of distilled water, heating the three-necked flask in a constant temperature oil bath to 60-65 deg.C, sequentially adding 46-60 parts of hexadecyl trimethyl ammonium bromide and ethylene glycol, controlling the solution mass fraction to be 10-15%, stirring at constant speed until the hexadecyl trimethyl ammonium bromide is completely dissolved, slowly dripping the solution in the reaction flask into the three-necked flask, and raising the temperature of the oil bath to 170-180 ℃ for reaction for 20-25 h, filtering the material after the reaction is finished to remove the solvent to obtain a solid product, washing the solid product by using a proper amount of distilled water and absolute ethyl alcohol in sequence, and placing the solid product in an oven for heating and drying to obtain the titanium dioxide nano rod.
5. According to the claimsThe metal organic framework photocatalytic hydrogen production composite material and the preparation method thereof according to claim 1 are characterized in that: the organic ligand is 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine with the formula C24H18N6O6Structural formula is
。
6. The metal organic framework photocatalytic hydrogen production composite material and the preparation method thereof according to claim 1, wherein the metal organic framework photocatalytic hydrogen production composite material is characterized in that: the preparation method of the metal organic framework photocatalytic hydrogen production composite material comprises the following steps:
(1) preparation of metal organic framework Hg3(TATAB)2Adding 200-300 mL of distilled water into a high-pressure hydrothermal automatic reaction kettle, weighing 40-52 parts of mercury sulfate, fully stirring uniformly, adding 400-700 mL of dimethyl sulfoxide and 18-22 parts of organic ligand 2,4, 6-tri [ (p-carboxyphenyl) amino group]-1,3, 5-triazine, setting a high-pressure hydrothermal automatic reaction kettle at 170 ℃, uniformly stirring and reacting for 25-30 h, cooling the reaction kettle to room temperature after the reaction is finished, filtering the material to remove the solvent, washing the material with appropriate amount of distilled water and ethyl acetate in turn, and drying in an oven to obtain the metal organic framework Hg3(TATAB)2;
(2) Preparation of Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material: adding 1000mL of anhydrous ethanol of 600-3(TATAB)2And 26-42 parts of titanium dioxide nano-rods, placing the beaker in a high-pressure hydrothermal automatic reaction kettle, raising the temperature to 120-130 ℃, stirring at constant speed for activation reaction for 3-6h, then transferring the materials in the reaction kettle into an ultrasonic treatment instrument, heating to 50-55 ℃ at the ultrasonic frequency of 25-28 KHz, and performing ultrasonic dispersion for 4-6 h to ensure that Hg is dispersed for 4-6 h3(TATAB)2Completely loaded on the surface and the inner wall of the titanium dioxide nano rod to obtain Hg3(TATAB)2Titanium dioxide nanorod photocatalytic hydrogen production composite material.
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