CN115463690B - Two-dimensional hierarchical pore bimetallic MOF photocatalyst and preparation method thereof - Google Patents
Two-dimensional hierarchical pore bimetallic MOF photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 36
- 239000013246 bimetallic metal–organic framework Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 21
- 239000002135 nanosheet Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- QMLILIIMKSKLES-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol Chemical compound C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 QMLILIIMKSKLES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 230000009466 transformation Effects 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 238000013032 photocatalytic reaction Methods 0.000 claims description 2
- 230000001131 transforming effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000003504 photosensitizing agent Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 33
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 229910003321 CoFe Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
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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
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- B01J35/39—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
Abstract
The invention discloses a two-dimensional hierarchical pore bimetallic MOF photocatalyst and a preparation method thereof, wherein the catalyst has a two-dimensional nano sheet layer and a hierarchical pore structure, which is expressed as MFeMOF, wherein M=Cu, co or Ni, and the ligand is 2,3,6,7,10, 11-hexahydroxybenzophenanthrene; the preparation method of the catalyst comprises the following steps: and carrying out topological transformation on the bimetallic oxide nano-sheet obtained by the sodium borohydride reduction method and 2, 5-dihydroxyterephthalic acid to obtain the two-dimensional hierarchical pore bimetallic MOF photocatalyst. The catalyst prepared by the invention can be applied to the photocatalysis of CO by normal temperature visible light 2 And (3) transformation. Under the condition of normal temperature gas-solid reaction without adding photosensitizer and electron donor, the catalyst has the characteristics of high catalytic activity, strong circulation stability and the like.
Description
Technical Field
The invention relates to a photocatalyst and a preparation method thereof, in particular to a two-dimensional hierarchical pore bimetallic MOF photocatalyst and a preparation method thereof.
Background
Photocatalytic, electrocatalytic and thermocatalytic reduction of CO 2 Is the most promising strategy to solve environmental problems and energy crisis. Efficient catalyst and sufficient energy for linear CO 2 Activation and conversion of the molecule is critical. Wherein, by utilizing solar energy and photocatalyst, in H 2 The conversion of solar energy into chemical energy is realized by CO under the participation of O 2 Reduction produces the ultimate goal of high value-added chemicals.
Metal Organic Frameworks (MOFs) are porous structures of periodic networks formed by self-assembly of metal ions and organic ligands. MOFs are widely used in the fields of photocatalysis and the like due to their large specific surface area, adjustable pore structure and functional adjustability. However, bulk MOFs also suffer from drawbacks in that, due to the close association and rigid conjugation of the organic ligand and the metal node, MOFs can create photogenerated carrier separation and diffusion processes at the catalyst surface, transferring electrons from the ligand to the metal node. However, since their unidirectional transfer is easily compounded, the process can be stopped, which is disadvantageous for photocatalysis. In addition, the metal utilization of bulk MOFs is low and the ion diffusion capacity is poor.
Disclosure of Invention
The invention aims to: the invention aims to provide a catalyst with high photocatalytic activity for CO 2 Two-dimensional hierarchical pore bimetallic MOF photocatalysts with reducing activity; the invention further aims at providing a preparation method of the two-dimensional hierarchical pore bimetallic MOF photocatalyst; another object of the present invention is to provide a method for preparing the two-dimensional hierarchical pore bimetallic MOF photocatalyst for photocatalytic CO in visible light 2 Use in conversion.
The technical scheme is as follows: the two-dimensional hierarchical pore bimetallic MOF photocatalyst has a two-dimensional nano sheet layer and a hierarchical pore structure, which is expressed as MFe MOF, wherein M=Cu, co or Ni, and the ligand is 2,3,6,7,10, 11-hexahydroxybenzophenanthrene. The two-dimensional MOFs have the typical characteristics of high aspect ratio, small thickness, large transverse area and the like. The MOFs material is reduced in thickness to an atomic scale, can inhibit electron-hole recombination and accelerate charge conversion, is beneficial to light absorption, is easy to generate defects and coordination unsaturated sites, increases the exposure of active sites, and adjusts a local electron structure.
The preparation method of the two-dimensional multistage pore bimetallic MOF photocatalyst comprises the step of obtaining the two-dimensional multistage pore bimetallic MOF photocatalyst through topological transformation between a bimetallic oxide nano sheet obtained by a sodium borohydride reduction method and 2,3,6,7,10, 11-hexahydroxybenzophenanthrene.
Further, the bimetal oxide nano-sheet is one of CuFe, coFe, niFe oxide nano-sheets.
Further, the preparation process of the bimetal oxide nano sheet comprises the following steps: dissolving two metal salts in water, and slowly adding sodium borohydride to obtain the bimetal oxide nano-sheet.
Further, the reaction process of the bimetallic oxide nano-sheet and 2,3,6,7,10, 11-hexahydroxybenzophenanthrene is as follows: reflux reaction is carried out on the two in DMF solvent; and naturally cooling the obtained product to room temperature, centrifuging, washing the product with DMF and ethanol respectively, and drying to obtain the two-dimensional multistage pore bimetallic MOF photocatalyst.
Further, one of the metal salts is any one of nitrate or chloride of Cu, co and Ni, and the other is Fe (NO 3 ) 3 ·9H 2 O。
Further, the molar ratio of the two metal salts is 3:1-1:3.
Further, the reflux reaction temperature is 100-150 ℃.
The two-dimensional hierarchical pore bimetallic MOF photocatalyst can be applied to visible light photocatalytic CO 2 And (3) transformation.
Further, the application process is that the photocatalyst is arranged on a quartz glass fiber film and is put into a photocatalytic reactor, and water is added dropwise; CO 2 And (3) blowing and replacing air in the reactor by gas, and carrying out photocatalytic reaction under the condition of visible light after balancing the dark environment for 10-60 min.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The catalyst has high photocatalytic CO 2 Reduction activity and good cycling stability; (2) The preparation method of the catalyst adopts an in-situ topology method, a two-dimensional multistage pore bimetallic MOF photocatalyst is constructed through a 2,3,6,7,10, 11-hexahydroxy triphenylene (HHTP) ligand and a planar bimetallic node, and the catalyst prepared by the method has narrow size distribution, regular channels, adjustable band gap and a designable charge transmission path, and can realize efficient and stable visible light photocatalysis CO under the condition of normal temperature gas-solid reaction without adding photosensitizer and electron donor 2 And (5) reduction.
Drawings
FIG. 1 is a scanning electron microscope image of a two-dimensional hierarchical pore CuFe MOF photocatalyst prepared in example 1;
FIG. 2 is a scanning electron microscope image of a two-dimensional hierarchical pore CoFe MOF photocatalyst prepared in example 2;
FIG. 3 is a scanning electron microscope image of a two-dimensional hierarchical pore NiFe MOF photocatalyst prepared in example 3;
FIG. 4 is a graph showing pore size distribution of a two-dimensional hierarchical pore bimetallic MOF photocatalyst prepared in examples 1-3.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
The catalyst disclosed by the invention is prepared according to the following steps:
1) A bimetallic salt solution was prepared by separately weighing 0.41g of copper nitrate and 0.808g of ferric nitrate in 50mL of water. 0.2g of sodium borohydride is weighed and dissolved in 20mL of water, and slowly added into the bimetallic salt solution dropwise under stirring, after reacting for 5min at 25 ℃, the two-dimensional CuFe oxide precursor is obtained by centrifugation, ethanol washing for 3 times and room temperature drying for 2 days.
2) 10mg of the two-dimensional multistage hole CuFe MOF photocatalyst obtained in the step 1) is dissolved in 40mL of DMF, 2mg 2,3,6,7,10,11-hexahydroxybenzophenanthrene is added and stirred for 3min, the mixture is placed in an oil bath at 120 ℃ for reaction for 1h, and the mixture is washed with DMF and ethanol for multiple times through centrifugation, and vacuum drying is carried out at 25 ℃ for 6h to obtain the two-dimensional multistage hole CuFe MOF photocatalyst.
3) 10mg of a two-dimensional hierarchical pore CuFe MOF photocatalyst was placed on a quartz glass fiber membrane and placed in a 100mL photocatalytic reactor, and 2mL of water was added dropwise. CO 2 The air in the replacement reactor is purged by gas, the photocatalysis reaction is carried out under the condition of visible light after the dark environment is balanced for 30min, the gas product is collected for chromatographic analysis after 3h, and the generation rate of CO is 10.2 mu mol g – 1 h –1 The CO formation rate after three cycles was 8.5. Mu. Mol g –1 h –1 。
Example 2
The catalyst disclosed by the invention is prepared according to the following steps:
1) A bimetallic salt solution was prepared by separately weighing 0.582g of cobalt nitrate and 0.808g of ferric nitrate in 50mL of water. 0.2g of sodium borohydride is weighed and dissolved in 20mL of water, and slowly added into the bimetallic salt solution dropwise under stirring, after reacting for 5min at 30 ℃, the two-dimensional CoFe oxide precursor is obtained by centrifugation, ethanol washing for 3 times and room temperature drying for 2 days.
2) 10mg of the two-dimensional multistage hole CoFe MOF photocatalyst obtained in the step 1) is dissolved in 40mL of DMF, 2mg 2,3,6,7,10,11-hexahydroxybenzophenanthrene is added and stirred for 3min, the mixture is placed in an oil bath at 120 ℃ for reaction for 1h, the mixture is washed with DMF and ethanol for multiple times through centrifugation, and the mixture is dried in vacuum at 25 ℃ for 6h to obtain the two-dimensional multistage hole CoFe MOF photocatalyst.
3) 10mg of two-dimensional hierarchical pore CoFe MOF photocatalyst was placed on a quartz glass fiber membrane and placed in a 100mL photocatalytic reactor, and 2mL of water was added dropwise. CO 2 The air in the replacement reactor is purged by gas, the photocatalysis reaction is carried out under the condition of visible light after the dark environment is balanced for 30min, the gas product is collected for chromatographic analysis after 3h, and the generation rate of CO is 11.6 mu mol g – 1 h –1 The CO formation rate after three cycles was 9.8. Mu. Mol g –1 h –1 。
Example 3
The catalyst disclosed by the invention is prepared according to the following steps:
1) A bimetallic salt solution was prepared by separately weighing 0.582g of nickel nitrate and 0.808g of ferric nitrate in 50mL of water. 0.2g of sodium borohydride is weighed and dissolved in 20mL of water, and slowly added into the bimetallic salt solution dropwise under stirring, after reacting for 5min at 25 ℃, the two-dimensional NiFe oxide precursor is obtained by centrifugation, ethanol washing for 3 times and room temperature drying for 2 days.
2) 10mg of the two-dimensional hierarchical pore NiFe MOF photocatalyst obtained in the step 1) is dissolved in 40mL of DMF, 2mg 2,3,6,7,10,11-hexahydroxybenzophenanthrene is added and stirred for 3min, the mixture is placed in an oil bath at 120 ℃ for reaction for 1h, and the two-dimensional hierarchical pore NiFe MOF photocatalyst is obtained by centrifugation, washing with DMF and ethanol for multiple times and vacuum drying at 30 ℃ for 12 h.
3) 10mg of a two-dimensional hierarchical pore NiFe MOF photocatalyst was placed on a quartz glass fiber membrane and placed in a 100mL photocatalytic reactor, and 2mL of water was added dropwise. CO 2 The air in the replacement reactor is purged by gas, the photocatalysis reaction is carried out under the condition of visible light after the dark environment is balanced for 30min, the gas product is collected for chromatographic analysis after 3h, and the generation rate of CO is 14.3 mu mol g – 1 h –1 The CO formation rate after three cycles was 12.6. Mu. Mol g –1 h –1 。
Example 4
The catalyst disclosed by the invention is prepared according to the following steps:
1) A bimetallic salt solution was prepared by separately weighing 0.291g of nickel nitrate and 0.808g of ferric nitrate in 50mL of water. 0.2g of sodium borohydride is weighed and dissolved in 20mL of water, and slowly added into the bimetallic salt solution dropwise under stirring, after reacting for 5min at 25 ℃, the two-dimensional NiFe oxide precursor is obtained by centrifugation, ethanol washing for 3 times and room temperature drying for 2 days.
2) 10mg of the two-dimensional hierarchical pore NiFe MOF photocatalyst obtained in the step 1) is dissolved in 40mL of DMF, 2mg 2,3,6,7,10,11-hexahydroxybenzophenanthrene is added and stirred for 3min, the mixture is placed in an oil bath at 130 ℃ for reaction for 1h, and the mixture is washed with DMF and ethanol for multiple times through centrifugation, and vacuum drying is carried out at 30 ℃ for 14 h to obtain the two-dimensional hierarchical pore NiFe MOF photocatalyst.
3) 10mg of a two-dimensional hierarchical pore NiFe MOF photocatalyst was placed on a quartz glass fiber membrane and placed in a 100mL photocatalytic reactor, and 2mL of water was added dropwise. CO 2 The air in the replacement reactor is purged by gas, the photocatalysis reaction is carried out under the condition of visible light after the dark environment is balanced for 30min, the gas product is collected for chromatographic analysis after 3h, and the generation rate of CO is 12.7 mu mol g – 1 h –1 The CO formation rate after three cycles was 10.7. Mu. Mol g –1 h –1 。
FIGS. 1-3 correspond to Scanning Electron Microscope (SEM) images of the two-dimensional hierarchical pore CuFe MOF, coFe MOF and NiFe MOF photocatalysts prepared in examples 1-3, respectively, and it can be seen that the two-dimensional hierarchical pore photocatalysts prepared by the method are of a two-dimensional lamellar stacking structure.
FIG. 4 is a graph showing pore size distribution of two-dimensional hierarchical pore bimetallic MOF photocatalysts CuFe MOF, coFe MOF and NiFe MOF prepared in examples 1-3, wherein the two-dimensional CuFe MOF, coFe MOF and NiFe MOF photocatalysts have microporous and mesoporous structures.
Claims (7)
1. The preparation method of the two-dimensional hierarchical pore bimetallic MOF photocatalyst comprises the steps of topologically converting a bimetallic oxide nano sheet obtained by a sodium borohydride reduction method with 2,3,6,7,10, 11-hexahydroxybenzophenanthrene to obtain the two-dimensional hierarchical pore bimetallic MOF photocatalyst;
the preparation process of the bimetal oxide nano sheet comprises the following steps: dissolving two metal salts in water, and adding sodium borohydride to obtain a bimetallic oxide nano-sheet; the reaction process of the bimetallic oxide nano-sheet and 2,3,6,7,10, 11-hexahydroxybenzophenanthrene comprises the following steps: and (3) carrying out reflux reaction on the two in DMF solvent, naturally cooling the obtained product to room temperature, centrifuging, washing the product with DMF and ethanol respectively, and drying to obtain the two-dimensional multistage pore bimetallic MOF photocatalyst.
2. A method for preparing a two-dimensional hierarchical pore bimetallic MOF photocatalyst according to claim 1, which is characterized in that the method comprises the steps of obtaining a two-dimensional hierarchical pore bimetallic MOF photocatalyst by topologically transforming a bimetallic oxide nano-sheet obtained by a sodium borohydride reduction method with 2,3,6,7,10, 11-hexahydroxybenzophenanthrene, wherein the bimetallic oxide nano-sheet is one of CuFe, coFe, niFe oxide nano-sheets;
the preparation process of the bimetal oxide nano sheet comprises the following steps: dissolving two metal salts in water, and adding sodium borohydride to obtain a bimetallic oxide nano-sheet; the reaction process of the bimetallic oxide nano-sheet and 2,3,6,7,10, 11-hexahydroxybenzophenanthrene comprises the following steps: and (3) carrying out reflux reaction on the two in DMF solvent, naturally cooling the obtained product to room temperature, centrifuging, washing the product with DMF and ethanol respectively, and drying to obtain the two-dimensional multistage pore bimetallic MOF photocatalyst.
3. According to claim 2The preparation method of the two-dimensional hierarchical pore bimetallic MOF photocatalyst is characterized in that one of the metal salts is any one of nitrate or chloride of Cu, co and Ni, and the other metal salt is Fe (NO 3 ) 3 ・9H 2 O。
4. The method for preparing a two-dimensional hierarchical pore bimetallic MOF photocatalyst according to claim 2, wherein the molar ratio of the two metal salts is 3:1-1:3.
5. The method for preparing a two-dimensional hierarchical pore bimetallic MOF photocatalyst according to claim 2, wherein the reflux reaction temperature is 100-150 ℃.
6. A two-dimensional hierarchical pore bimetallic MOF photocatalyst as claimed in claim 1 for photocatalytic CO in visible light 2 Use in conversion.
7. The two-dimensional hierarchical pore bimetallic MOF photocatalyst according to claim 6 for photocatalytic CO in visible light 2 The application in the transformation is characterized by comprising the steps of placing the photocatalyst on a quartz glass fiber membrane, placing the quartz glass fiber membrane into a photocatalytic reactor, and dropwise adding water; CO 2 And (3) blowing and replacing air in the reactor by gas, and carrying out photocatalytic reaction under the condition of visible light after balancing the dark environment for 10-60 min.
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| WO2020037310A1 (en) * | 2018-08-17 | 2020-02-20 | Trustees Of Dartmouth College | Conductive bimetallic metal-organic frameworks for the detection of analytes |
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| CN114849721A (en) * | 2022-05-19 | 2022-08-05 | 江南大学 | S-type Bi for efficiently degrading organic wastewater 2 O 3 /CuO heterojunction visible-light-driven photocatalyst and preparation method thereof |
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| CN114177923A (en) * | 2021-11-05 | 2022-03-15 | 大连理工大学 | Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nano material, preparation method and application |
| CN114849721A (en) * | 2022-05-19 | 2022-08-05 | 江南大学 | S-type Bi for efficiently degrading organic wastewater 2 O 3 /CuO heterojunction visible-light-driven photocatalyst and preparation method thereof |
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