CN117899937A - Layered CO of molecular size2Reduction catalyst, preparation method and application thereof - Google Patents
Layered CO of molecular size2Reduction catalyst, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 79
- 235000019253 formic acid Nutrition 0.000 claims abstract description 40
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 12
- KJAMXGRVUWOPLJ-UHFFFAOYSA-N benzoic acid pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34.C(C3=CC=CC=C3)(=O)O KJAMXGRVUWOPLJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 23
- 230000001699 photocatalysis Effects 0.000 claims description 23
- 239000000523 sample Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000003780 insertion Methods 0.000 claims description 5
- 230000037431 insertion Effects 0.000 claims description 5
- 239000003504 photosensitizing agent Substances 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000004299 exfoliation Methods 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000010941 cobalt Substances 0.000 abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 description 29
- 239000013078 crystal Substances 0.000 description 17
- 239000012621 metal-organic framework Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000002356 single layer Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000004255 ion exchange chromatography Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013208 UiO-67 Substances 0.000 description 3
- -1 aromatic pyrene nucleus Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
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- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
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- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
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- 238000012430 stability testing Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
The invention belongs to the technical field of CO 2 reduction catalytic materials, and particularly relates to a layered CO 2 reduction catalyst with molecular size, a preparation method and application thereof, wherein the catalyst is a two-dimensional layered MOF material formed after 1,3,6, 8-tetra (4-carboxybenzene) pyrene is firstly used as a ligand and is coordinated with Co 2+; and then stripping the two-dimensional layered MOF material into a monomolecular layer structure through ultrasonic stripping. According to the invention, the MOF material with a layered structure is obtained by coordination of H 4 TBAPy and cobalt, and the material with the two-dimensional structure is further peeled into a monomolecular layer structure, so that the selective capture of CO 2 under the condition of mixed gas is realized, and the reduction of CO 2 into formic acid can be efficiently and photocatalysed.
Description
Technical Field
The invention belongs to the technical field of CO 2 reduction catalytic materials, and particularly relates to a layered CO 2 reduction catalyst with molecular size, a preparation method and application thereof.
Background
With the proliferation of human industrial activities and the increase of fossil energy consumption, carbon dioxide (CO 2) emissions are increasing. An effective solution to mitigate global warming and energy crisis is to store or convert CO 2 into other high value chemicals.
Reduction of CO 2 to carbonaceous fuels or high value chemicals using solar energy is considered a sustainable route to energy production and is the most promising method to mitigate the greenhouse effect. However, reduction of CO 2 presents the following difficulties: CO 2 is very stable at normal temperature and normal pressure, and has stronger chemical inertness. The carbon atom of CO 2 is in the highest oxidation state (+4 valence) and the carbon-oxygen double bond has a higher bond energy (750 kJ/mol) making the chemical bond of CO 2 extremely difficult to break and difficult to form new chemicals.
Disclosure of Invention
In order to solve the technical problems, the invention provides a layered CO 2 reduction catalyst with molecular size, a preparation method and application thereof, wherein a MOF material with a layered structure is obtained by coordinating a1, 3,6, 8-tetra (4-carboxybenzene) pyrene ligand and cobalt, and the material with a two-dimensional structure is further peeled into a monolayer structure, so that CO 2 is selectively captured under the condition of mixed gas, CO 2 can be efficiently reduced into formic acid by photocatalysis, and the problem that CO 2 is difficult to reduce is solved.
The invention is realized by the following technical scheme.
The invention provides a layered CO 2 reduction catalyst with molecular size, which is a two-dimensional layered MOF material formed after 1,3,6, 8-tetra (4-carboxybenzene) pyrene is taken as a ligand and is coordinated with Co 2+; and then stripping the two-dimensional layered MOF material into a monomolecular layer structure through ultrasonic stripping.
The preparation method of the layered CO 2 reduction catalyst with the molecular size comprises the following steps:
dissolving 1,3,6, 8-tetra (4-carboxylbenzenepyrene) ligand and soluble cobalt salt in a solvent, and carrying out ultrasonic treatment to prepare a solution I;
adding water and nitric acid into the solution I, and performing ultrasonic treatment to prepare solution II;
Cobalt in the structure is coordinated with an organic ligand in a form of a cluster compound of Co 3O16, and cobalt oxide clusters can be formed by adding water and nitric acid, so that delocalized electron orbitals of the cluster compound are more beneficial to charge separation in the photocatalysis process, and the catalytic performance is improved.
Placing the solution II in a sealed environment, reacting at 110-120 ℃, and cooling to room temperature after the reaction is finished to obtain a crude product; washing the crude product, and drying to obtain a two-dimensional layered MOF material;
The two-dimensional layered MOF material obtained was exfoliated into a catalyst having a monomolecular layer structure by ultrasonic exfoliation.
Further, the soluble cobalt salt is Co (NO 3)2·6H2O,CoCl2·6H2 O or Co (CH 3COO)2·4H2 O).
Further, the molar ratio of the 1,3,6, 8-tetra (4-carboxylbenzenepyrene) ligand to the soluble cobalt salt is 1:2.
Further, the solvent is DMF.
Further, the mass fraction of nitric acid is 68%, and the dosage ratio of the 1,3,6, 8-tetra (4-carboxylbenzenepyrene) ligand, water and nitric acid is 6.6-6.9mg:1mL:10-13.3 mu L.
Further, the reaction time was 48 hours.
Further, the specific operation of ultrasonic stripping is as follows: grinding the two-dimensional layered MOF material, and mixing with acetonitrile after grinding to obtain a dispersion liquid; the ultrasonic probe is inserted into the dispersion liquid in the beaker, the insertion depth is 1 cm to 2cm below the liquid level, the ultrasonic power is 200W, and the ultrasonic time is 4 hours, and the obtained dispersion liquid is a product of a monomolecular layer structure.
The invention also provides application of the catalyst in a reaction of catalyzing CO 2 to reduce into formic acid, under the condition of visible light, acetonitrile is used as a reaction solvent, triethanolamine is used as a sacrificial agent, ruthenium bipyridine is used as a photosensitizer, and the catalyst is used for catalyzing CO 2 to reduce into formic acid.
Compared with the prior art, the invention has the following beneficial effects:
The 1,3,6, 8-tetra (4-carboxybenzene) pyrene ligand (H 4 TBAPy) is a fluorescent molecule with pi conjugated aromatic pyrene nucleus, has the characteristics of high conjugated big pi bond, strong CO 2 adsorption selectivity, optical property, excellent charge transfer capability and the like, and the invention prepares a MOF material with a layered structure by coordinating H 4 TBAPy and cobalt, and further strips the material with a two-dimensional structure into a monomolecular layer structure, thereby realizing selective capture of CO 2 under the condition of mixed gas and efficiently catalyzing CO 2 to reduce formic acid.
The catalyst has a thickness of 1nm sheet after stripping, and more catalytic sites are exposed, thereby being beneficial to the photocatalytic carbon dioxide reduction reaction.
Under the condition of visible light, acetonitrile is used as a reaction solvent, triethanolamine is used as a sacrificial agent, ruthenium bipyridine is used as a photosensitizer, and stripped catalyst is used for photocatalytic CO 2 reduction to generate formic acid, and the catalytic efficiency is higher than that of MOFs materials such as Co-UiO-67, MIL-125-NH 2, PCN-136 and the like.
The preparation method is simple in raw materials, simple and convenient in preparation method, easy to implement, high in catalytic efficiency of the prepared catalyst and suitable for large-scale application.
Drawings
FIG. 1a is a coordinated environment of HTBAPy 3- ligands; b is the coordination environment of Co 3 clusters, wherein Co1 is positioned at the center position; c is a conical octahedral structure formed by Co 3 clusters; d is a single layer stacked structure along the c-axis; e is a bilayer stacked structure along the a-axis (Co, purple; O, red; C, grey. Hydrogen atoms and solvent molecules are omitted for clarity).
FIG. 2a is a PXRD diagram of a Co-TBAPy sample; b is a Transmission Electron Microscope (TEM) of the non-ultrasonically peeled sample; c is a transmission electron microscope image of the sample processed by the ultrasonic cell grinder; d is STEM picture and distribution diagram of C, O and Co elements.
FIG. 3a is a schematic view of ultrasonic peeling; b. and c is an atomic force spectrum and the corresponding thickness of the sample after stripping.
FIG. 4 is an Ion Chromatography (IC) detection of liquid phase products formed in a photocatalytic system.
FIG. 5 a is the amount of formic acid produced in CO 2 by the catalyst without ultrasonic stripping under dark and light conditions, and the amount of formic acid produced in CO 2 and the mixed gas by the stripped catalyst; b is the amount of formic acid generated by cycling and catalyzing the catalyst for 3 times with 10h as one period; c is the photoresponse current of Co-TBAPy; d is the comparison of the front and rear PXRD of Co-TBAPy photocatalysis.
FIG. 6a is a diagram of a 12 C nuclear magnetic resonance of Co-TBAPy to produce formic acid; b is 13 C nuclear magnetism of 13CO2 carbon source to generate formic acid.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
CO 2 is very stable at normal temperature and normal pressure, and has stronger chemical inertness. The carbon atom of CO 2 is in the highest oxidation state (+4 valence) and the carbon-oxygen double bond has a higher bond energy (750 kJ/mol) making the chemical bond of CO 2 extremely difficult to break and difficult to form new chemicals.
According to the invention, the MOF material with a layered structure is obtained by coordination of H 4 TBAPy and cobalt, and the material with a two-dimensional structure is further stripped into a monomolecular layer structure, and the stripped catalyst has a thickness of 1nm and exposes more catalytic sites, thereby being beneficial to photocatalytic carbon dioxide reduction reaction. Under the condition of visible light, acetonitrile is used as a reaction solvent, triethanolamine is used as a sacrificial agent, ruthenium bipyridine is used as a photosensitizer, and stripped catalyst is used for photocatalytic CO 2 reduction to generate formic acid, and the catalytic efficiency is higher than that of MOFs materials such as Co-UiO-67, MIL-125-NH 2, PCN-136 and the like.
The following examples and comparative examples are provided to illustrate the present invention.
Example 1
A method for preparing a layered CO 2 reduction catalyst of molecular size, comprising the steps of:
10.25mg of H 4 TBAPy and 20.35mg of Co (NO 3)2·6H2 O are dissolved in 2.5mL of DMF, ultrasonic treatment is carried out for 10min, 1.5mL of water and 20 mu L of commercial concentrated nitric acid (cobalt in the structure is coordinated with an organic ligand in the form of a cluster of Co 3O16, cobalt oxide clusters can be formed by adding water and nitric acid, delocalized electron orbitals of the cluster are more beneficial to charge separation in the photocatalysis process, and the catalysis performance is improved), ultrasonic treatment is carried out for 5min again to uniformly disperse and stir the solution for 10min, and then the solution is transferred into a 20mL headspace glass bottle, sealing is carried out, then the solution is put into an oven for reaction for 48H at 110 ℃, pink transparent crystals are obtained after cooling to room temperature, the crystals are collected and washed to be colorless, the crystals are washed and soaked for three days with acetonitrile, and vacuum drying is carried out for 12H at 60 ℃, so that 16.61mg of pink sample is Co-TBAPy, the molecular formula C 104.8H25.2N5.6O25.6Co3, and the yield is 56.8%.
Ultrasonic peel (a in fig. 3): grinding 50mgCo-TBAPy in agate mortar for 15min, taking out the ground powder, adding into 200mL beaker containing 100mL acetonitrile, inserting ultrasonic probe into acetonitrile dispersion liquid in beaker, the insertion depth is 1cm below liquid level, ultrasonic power is 200w, ultrasonic time is 4 hr, the obtained dispersion liquid is monomolecular layer two-dimensional MOF dispersion liquid, atomic force test shows that the thickness of layer is about 1nm (as shown in b and c in figure 3), which is consistent with the size of single-layer MOF in crystal structure. The prepared dispersion liquid can be directly used for photocatalytic reduction of CO 2.
Example 2
A method for preparing a layered CO 2 reduction catalyst of molecular size, comprising the steps of:
Taking 20mg of H 4 TBAPy and 40mg of Co (NO 3)2·6H2 O dissolved in 10mL of DMF, carrying out ultrasonic treatment for 10min, adding 3mL of water and 30 mu L of concentrated sulfuric acid, continuously stirring for 30min, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, sealing, putting into a baking oven for reaction at 120 ℃ for 48H, cooling to room temperature to obtain pink transparent crystals, collecting the crystals, washing the crystals with ethanol to be colorless, and carrying out vacuum drying at 60 ℃ for 12H to obtain 33mg of pink sample which is Co-TBAPy, wherein the molecular formula is C 104.8H25.2N5.6O25.6Co3, and the yield is 56.9%.
Ultrasonic stripping conditions: 10mgCo-TBAPy is put into an agate mortar for grinding for 15 minutes, the ground powder is taken out and added into a 100mL beaker containing 50mL acetonitrile, an ultrasonic probe is inserted into acetonitrile dispersion liquid in the beaker by ultrasonic wave, the insertion depth is 2cm below the liquid level, the ultrasonic power is 200w, the ultrasonic time is 4 hours, the obtained dispersion liquid is monomolecular layer two-dimensional MOF dispersion liquid, and atomic force test shows that the thickness of a layer is about 1nm, which is consistent with the size of single-layer MOF in a crystal structure. The prepared dispersion liquid can be directly used for photocatalytic reduction of CO 2.
Example 3
A method for preparing a layered CO 2 reduction catalyst of molecular size, comprising the steps of:
Taking 10.25mg of H 4 TBAPy and 20.35mg of Co (NO 3)2·6H2 O is dissolved in 2.5mL of DMF, carrying out ultrasonic treatment for 10min, adding 1.5mL of water and 20 mu L of concentrated nitric acid, carrying out ultrasonic treatment again for 10min to uniformly disperse the solution, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, sealing, placing the reaction kettle into an oven to react at 120 ℃ for 48H, cooling to room temperature to obtain pink transparent crystals, washing the pink transparent crystals to be colorless by acetonitrile and soaking the pink transparent crystals for three days, and carrying out vacuum drying at 60 ℃ for 12H to obtain about 16mg of pink samples which are the Co-TBAPy, wherein the molecular formula is C 104.8H25.2N5.6O25.6Co3, and the yield is 57.1%.
Ultrasonic stripping conditions: grinding 5mgCo-TBAPy in agate mortar for 15min, taking out the ground powder, adding the ground powder into a 50mL beaker containing 30mL acetonitrile, inserting an ultrasonic probe into ethanol dispersion liquid in the beaker, wherein the insertion depth is 2cm below the liquid level, the ultrasonic power is 200w, the ultrasonic time is 3h, the obtained dispersion liquid is monomolecular layer two-dimensional MOF dispersion liquid, and atomic force test shows that the thickness of the layer is about 1nm, which is consistent with the size of single-layer MOF in a crystal structure. The prepared dispersion liquid can be directly used for photocatalytic reduction of CO 2.
Comparative example 1
Co-tbapey without ultrasonic exfoliation comprising the steps of:
Taking 10.25mg of H 4 TBAPy and 20.35mg of Co (NO 3)2·6H2 O is dissolved in 2.5mL of DMF, carrying out ultrasonic treatment for 10min, adding 1.5mL of water and 20 mu L of concentrated nitric acid (cobalt in the structure is coordinated with an organic ligand in the form of a cluster compound of Co 3O16, the addition of water and nitric acid can form cobalt oxide clusters, the delocalized electron orbitals of the cluster compound are more beneficial to charge separation in the photocatalysis process, and the catalytic performance is improved), carrying out ultrasonic treatment for 5min again to uniformly disperse and stir the solution for 10min, transferring the solution into a 20mL headspace glass bottle, sealing, putting the headspace glass bottle into an oven for reaction at 110 ℃ for 48H, cooling to room temperature to obtain pink transparent crystals, collecting the crystals, washing the crystals with DMF to be colorless, soaking the crystals for three days, carrying out vacuum drying at 60 ℃ for 12H, and obtaining 16.61mg of pink sample, namely Co-TBAPy, wherein the molecular formula is C 104.8H25.2N5.6O25.6Co3, and the yield is 56.8%.
The catalyst structures and properties prepared in examples 1-3 above are similar, and the materials prepared will be described in characterization by taking example 1 alone as an example and comparative example 1 as a control.
(1) Structural characterization of materials
The phase purity of Co-TBAPy was analyzed by PXRD, and the result showed that the diffraction peak of the sample was substantially identical to that of single crystal simulation, and only the intensity was different, demonstrating that the mass-prepared sample was pure phase.
After the material was subjected to TEM characterization, it can be seen from TEM images (b, c in FIG. 2) that the Co-TBAPy that was not ultrasonically peeled off in comparative example 1 was in a larger block shape, whereas the sample peeled off by the ultrasonic cell grinder in example 1 exhibited a thinner layer shape.
EDS analysis was also performed on the material, indicating that C, O, co elements were uniformly dispersed and densely distributed (d in fig. 2).
The thickness analysis of the sample after ultrasonic peeling was performed, and the atomic force diagram shows that the sample forms a 1nm sheet after ultrasonic peeling, which is consistent with the thickness of a single layer, and proves that the sample is peeled into a single layer shape after ultrasonic peeling (b and c in fig. 3). Compared with the former, the sample after stripping exposes more catalytic sites, which is beneficial to the photocatalytic carbon dioxide reduction reaction.
(2) The catalytic performance of the catalyst was characterized as follows
The liquid phase product from electrocatalytic CO 2 was analyzed by anion chromatography and the faraday efficiency of the catalyst was calculated from the following formula:
Wherein F is Faraday constant and has a value of 96485C/mol; n is the molar amount of formic acid; 2 is the number of electrons required for conversion of CO 2 to HCOOH; q is the amount of electricity consumed during the reaction.
TOF is the conversion of the catalyst to reduce CO 2 to formic acid in each hour and is calculated as follows:
I product is the fractional current density to generate formic acid; n is the number of electrons required for CO 2 to be converted into formic acid, and the value is 2; f is Faraday constant and has a value of 96485C/mol; m cat is the mass of catalyst in the electrode; omega is the mass fraction of metal and M metal is the mass of metal atoms.
Based on the theoretical calculation, we further explore the photocatalytic CO 2 reduction reaction performance of the catalyst. Under the condition of visible light, acetonitrile is used as a reaction solvent, triethanolamine is used as a sacrificial agent, ruthenium bipyridine is used as a photosensitizer, and 5mg of catalyst is used for carrying out photocatalytic CO 2 reduction performance test. The liquid phase product of the photocatalytic CO 2 reduction was detected using Ion Chromatography (IC) and the gas phase product of the photocatalytic process was detected by Gas Chromatography (GC). We conducted photocatalytic performance studies on the sample that was not sonicated (comparative example 1) and the sample after treatment with the ultrasonic cell disruptor (example 1) under high purity CO 2 and simulated smoke conditions, respectively. The catalyzed reduction product was examined by IC and GC chromatography under the same photocatalytic conditions, and no gas phase reduction product was found but a liquid phase reduction product was found, which was formic acid (fig. 4).
Based on the above results, the photocatalytic activity of the sample before and after ultrasonic peeling was further investigated. Under irradiation with visible light we tested the catalyst for formic acid yield over 10h and further elucidated the relationship between the light irradiation time and formic acid yield, respectively.
As shown in FIG. 5a, co-TBAPy of comparative example 1, which was not ultrasonically peeled, was free from formic acid under dark conditions, and the amount of formic acid catalytically produced within 10 hours was only 1.5mmol/g. In example 1, co-TBAPy after stripping was not detected at any product under dark conditions for 2 hours. The amount of formic acid generated by illumination for 2 hours is 2.24mmol/g without changing other external conditions, and the yield of formic acid is continuously increased along with the increase of illumination time, and the amount of formic acid in 10 hours reaches 5.28mmol/g. This result demonstrates that the catalyst only catalyzes the reduction of CO 2 to formic acid under photoinduced conditions, that the Co-TBAPy catalyst stripped to a monolayer has an approximately 5-fold higher efficiency than the unpeeled formic acid production, and that the catalytic efficiency is higher than MOFs materials such as Co-UiO-67, MIL-125-NH 2, PCN-136, etc.
As can be seen from the transmission electron microscope, the stripped sample is changed into a thin layer from a block structure, so that the photocatalytic carbon dioxide reduction performance of the catalyst is greatly improved. To further investigate the catalytic activity, we tested the catalytic effect of the catalyst in a mixed gas (CO 2:14.7％;N2:77.5％;O2: 7.8%). In FIG. 5a is the amount of formic acid produced per gram of catalyst in 10 hours during which CO 2 is reduced. The generation rate of formic acid is fastest within 0-2 h and reaches 1.7mmol/g, then the generation rate is stable, the total amount of formic acid within 6h reaches 3.3mmol/g, the amount of formic acid within 10h is 4.83mmol/g, and the result is slightly lower than the catalytic effect of high-purity CO 2.
The number of conversions and the frequency of conversions for the catalyst were calculated from the above data, and the specific values are shown in table 1. Under the condition of visible light, the amount of formic acid produced by catalyzing CO 2 reduction by 5mg of the catalyst in 10h is 26.4 mu mol (5.28 mmol/g), the conversion number of the catalyst is 8.44, and the conversion frequency is 0.84h -1. In Co-TBAPy, co1 is in a saturated coordination state of 6 coordination, does not participate in the catalytic reduction process of CO 2, and only Co2 with equal amounts at two ends participates in the reduction process. Thus, the number of conversions per metal catalytically active site was 4.22. The catalyst was subjected to stability testing in acetonitrile solution with a cycle period of 10 h. As can be seen from FIG. 5b, the yield of formic acid was reduced under the same conditions after three cycles, but the activity was still higher. In FIG. 5d, it is shown that Co-TBAPy has not changed its structure after the photocatalytic reaction.
TABLE 1 amount and conversion efficiency of catalyst Co-TBAPy to formic acid under light sources of different wavelengths and powers
| Monochromatic light(λ) | 405nm | 504nm | 526nm |
| Light intensity(mW·cm-2) | 39.6 | 25.3 | 26.8 |
| HCOO(μmol) | 61.3 | 45.15 | 70.39 |
| QE％ | 0.096％ | 0.089％ | 0.13％ |
To confirm that the formic acid formed was derived from CO 2, we performed 13CO2 isotope calibration on Co-TBAPy under the same photocatalytic reaction conditions and determined the formic acid source by 13 C NMR chromatography. As can be seen in fig. 6, 13 C NMR spectrum showed a clear signal peak at 164.7 ppm. When the carbon source was 12CO2, no signal peak for formic acid was observed other than the corresponding CH 3 CN, TEOA and tritiated DMSO peaks, and the nuclear magnetic results demonstrated that formic acid was indeed produced by Co-TBAPy catalyzed CO 2 reduction after stripping.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that such modifications and variations be included herein within the scope of the appended claims and their equivalents.
Claims (10)
1. The molecular-size laminar CO 2 reduction catalyst is characterized in that 1,3,6, 8-tetra (4-carboxybenzene) pyrene is taken as a ligand, and is coordinated with Co 2+ to form a two-dimensional laminar MOF material; and then stripping the two-dimensional layered MOF material into a monomolecular layer structure through ultrasonic stripping.
2. The method for preparing a molecular-sized layered CO 2 reduction catalyst according to claim 1, comprising the steps of:
dissolving 1,3,6, 8-tetra (4-carboxylbenzenepyrene) ligand and soluble cobalt salt in a solvent, and carrying out ultrasonic treatment to prepare a solution I;
adding water and nitric acid into the solution I, and performing ultrasonic treatment to prepare solution II;
placing the solution II in a sealed environment, reacting at 110-120 ℃, and cooling to room temperature after the reaction is finished to obtain a crude product; washing the crude product, and drying to obtain a two-dimensional layered MOF material;
The two-dimensional layered MOF material obtained was exfoliated into a catalyst having a monomolecular layer structure by ultrasonic exfoliation.
3. The method of claim 2, wherein the soluble cobalt salt is Co (NO 3)2·6H2O、CoCl2·6H2 O or Co (CH 3COO)2·4H2 O).
4. The method of claim 3, wherein the molar ratio of 1,3,6, 8-tetrakis (4-carboxylbenzenepyrene) ligand to soluble cobalt salt is 1:2.
5. The method of claim 2, wherein the solvent is DMF.
6. The preparation method according to claim 2, wherein the mass fraction of nitric acid is 68%, and the ratio of the 1,3,6, 8-tetrakis (4-carboxylbenzene) pyrene ligand, water and nitric acid is 6.6-6.9mg:1mL:10-13.3 mu L.
7. The preparation method according to claim 2, wherein the reaction time is 48 hours.
8. The preparation method according to claim 2, wherein the specific operation of ultrasonic stripping is: grinding the two-dimensional layered MOF material, and mixing with acetonitrile after grinding to obtain a dispersion liquid; the ultrasonic probe is inserted into the dispersion liquid, the insertion depth is 1-2cm below the liquid level, the ultrasonic power is 200W, and the ultrasonic time is 4 hours, and the obtained dispersion liquid is a product of a monomolecular layer structure.
9. Use of the catalyst according to claim 1 for catalyzing the reduction of CO 2 to formic acid.
10. The use according to claim 9, wherein under visible light conditions, acetonitrile is used as a reaction solvent, triethanolamine is used as a sacrificial agent, ruthenium bipyridine is used as a photosensitizer, and the catalyst is used for photocatalytic reduction of CO 2 to form formic acid.
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