CN114570369B - MOFs derived nano-sheet self-assembled hierarchical double-layer hollow nano-material and preparation method thereof - Google Patents
MOFs derived nano-sheet self-assembled hierarchical double-layer hollow nano-material and preparation method thereof Download PDFInfo
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- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001338 self-assembly Methods 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 238000006722 reduction reaction Methods 0.000 abstract description 16
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- 229910003266 NiCo Inorganic materials 0.000 description 2
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/23—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a MOFs derived nano-sheet self-assembled hierarchical double-layer hollow NiCoO nano-rod material and a preparation method thereof.The method comprises the following steps: adding a surfactant into the metal salt solution, heating, stirring, centrifuging and drying to obtain a Co precursor material; dispersing a Co precursor material to obtain a Co precursor suspension, adding an organic ligand solution into the solution, heating, stirring, centrifuging and drying to obtain a Co-ZIF nano rod material; adding Ni solution into Co-ZIF solution, heating, centrifuging, drying and calcining to obtain the nano-sheet self-assembled hierarchical double-layer hollow NiCoO nano-rod material. The invention takes Co-based MOFs as a precursor, prepares the nano-sheet self-assembled hierarchical double-layer hollow NiCoO nano-rod material by methods of self-template derivatization, hydrothermal treatment, pyrolysis and the like, and has simple operation, safety and environmental protection compared with the traditional template method; meanwhile, due to the introduction of the bimetallic locus, the material is used for photocatalysis of CO 2 The reduction reaction shows excellent activity and selectivity, and has good application prospect.
Description
Technical Field
The invention relates to the field of nano hollow materials, in particular to a MOFs derived nano-sheet self-assembled hierarchical double-layer hollow nano material and a preparation method thereof.
Background
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) are a new class of porous zeolite-like materials that have emerged in recent years, being three-dimensional porous materials with regular pore channels that self-assemble by coordination bonds from central Metal ions or Metal clusters and organic ligands. Compared with the traditional porous material, the MOFs material has high specific surface area, controllable pore diameter and adjustable morphology. The MOFs material can be prepared into a porous metal-carbon composite material with good thermal stability and chemical stability through pyrolysis, and has wide application prospect in the field of catalysis.
MOFs have been used in recent years as precursors to synthesize hollow nanomaterials with unique multishells due to their unique spatial structure and tunable chemical composition. However, one of the major problems facing today is: the multi-shell structure is usually constructed by means of strong acid and strong alkali auxiliary etching or externally adding a hard template and the like, the steps are complex and the conditions are harsh, and the application of the MOFs derivative material in the catalysis field is limited to a certain extent. Meanwhile, the hollow nano material obtained by directly calcining the MOFs material has simpler structural components, so that the selectivity of a catalytic reaction product is poor. Therefore, the method for preparing the double-layer hollow structure nano material is a challenge for material researchers, and is also a higher requirement for the field of MOFs materials by social development requirements.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a MOFs derived nano-sheet self-assembled hierarchical double-layer hollow nano-rod material and a preparation method thereof.
The object of the invention is achieved by at least one of the following technical solutions.
The preparation method of the MOFs derived nano-sheet self-assembled hierarchical double-layer hollow nano-rod material provided by the invention comprises the following steps of:
(1) Co (C) 2 H 3 O 2 ) 2 And a surfactant are dissolved in ethanol to obtain a mixed solution;
(2) Heating and stirring the mixed solution obtained in the step (1), and centrifugally drying to obtain a Co precursor;
(3) Adding the Co precursor in the step (2) into ethanol, and uniformly dispersing by ultrasonic waves to obtain a suspension A; dispersing an organic ligand in ethanol to obtain a solution B; mixing the suspension A with the solution B, heating, stirring, centrifuging and drying to obtain a Co-ZIF material;
(4) Adding ethanol into the Co-ZIF material in the step (3), and uniformly dispersing by ultrasonic to obtain a suspension C; ni (NO) 3 ) 2 ·6H 2 O is dissolved in water to obtain solution D; and mixing the suspension C with the solution D, heating, stirring, centrifugally drying, and calcining to obtain the MOFs-derived nano-sheet self-assembled hierarchical double-layer hollow NiCoO nano-rod material.
Further, the surfactant in the step (1) is polyvinylpyrrolidone, and the mass ratio of the metal salt to the surfactant is 1:6-5:1.
Further, the temperature of heating and stirring in the step (2) is 60-110 ℃, and the time of heating and stirring is 1-2h.
Further, the concentration of the suspension A in the step (3) is 2-8g/L.
Further, the organic ligand in the step (3) is 2-methylimidazole, and the concentration of the organic ligand is 0.2-0.8mol/L.
Further, the temperature of heating and stirring in the step (3) is 80-120 ℃, and the time of heating and stirring is 2-4h.
Further, the concentration of the suspension C in the step (4) is 0.2-0.6g/L, and the concentration of the solution D is 0-0.1mol/L.
Further, the heating temperature in the step (4) is 80-90 ℃, and the heating time is 5-20min.
Further, the calcining treatment in the step (4) adopts an air atmosphere; the calcination temperature is 250 ℃, the calcination treatment time is 2 hours, and the heating rate is 3 ℃/min.
The invention provides a MOFs derived nano-sheet self-assembled hierarchical double-layer hollow nano-rod material prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method provided by the invention is simple to operate, green and environment-friendly, and the self-template is a nano material with low cost and simple preparation;
(2) According to the preparation method provided by the invention, the double-layer hollow structure assembled by the nano-sheets obtained by in-situ hydrothermal derivatization of MOFs (metal-organic frameworks) can be effectively maintained after pyrolysis, and excellent activity and stability are shown in a photocatalysis experiment;
(3) According to the preparation method provided by the invention, the nickel element is introduced in the preparation process, so that the selectivity of the carbon monoxide product is further effectively improved on the basis of maintaining the original advanced nano structure and catalytic activity, and the preparation method has high practical application value.
Drawings
FIG. 1 is an SEM image of a Co precursor material obtained in example 1;
FIG. 2 is an SEM photograph of a Co-ZIF material obtained in example 1;
FIG. 3 is a TEM image of the 1#NiCoO material obtained in example 1;
FIG. 4 is a TEM image of the 1#NiCoO material obtained in example 1;
FIG. 5 is a PXRD curve of the 1#NiCoO material obtained in example 1, the 1#NiCoO material obtained in example 2, and the 3#NiCoO composite material obtained in example 3;
FIG. 6 is an SEM photograph of a Co precursor material obtained in example 4;
FIG. 7 is an SEM photograph of a Co precursor material obtained in example 5;
FIG. 8 is an SEM photograph of a Co-ZIF material obtained in example 6;
FIG. 9 is an SEM photograph of a Co-ZIF material obtained in example 7;
FIG. 10 is a photo-catalytic CO of 1#NiCoO material obtained in example 1 2 And a reduction reaction performance test result graph.
FIG. 11 is a 3#NiCoO material photocatalytic CO obtained in example 3 2 And a reduction reaction performance test result graph.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but are not intended to limit the practice and protection of the invention. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
Example 1
The embodiment provides a preparation method of MOFs derived nano-sheet self-assembly hierarchical double-layer hollow nano-rod material, which comprises the following steps:
(1) 0.5g Co (C) 2 H 3 O 2 ) 2 Adding 0.5g of surfactant into 200mL of ethanol, and performing ultrasonic dispersion for 5min to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) at 85 ℃ for 2 hours to obtain Co precursor suspension, centrifugally separating the obtained Co precursor suspension, fully washing with ethanol, and finally drying in a 60 ℃ oven for 12 hours to obtain a Co precursor material;
(3) Weighing 20mg of the Co precursor obtained in the step (2), dispersing into 10mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain pink suspension A; adding 4.0g of organic ligand into 150mL of ethanol for dissolution to obtain colorless transparent solution B; mixing the suspension A with the solution B, heating at 110 ℃ for 2 hours to obtain Co-ZIF suspension, centrifuging the obtained Co-ZIF suspension for 1min at 4000r/min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12 hours to obtain a Co-ZIF material;
(4) Weighing 40mg of the Co-ZIF material obtained in the step (3), dispersing the Co-ZIF material into 80mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain a suspension C; 182mgNi (NO) 3 ) 2 ·6H 2 O is dissolved in 10mL of water to obtain solution D; mixing the suspension C with the solution D, heating at 85 ℃ for 5min to obtain NiCo-LDH suspension, centrifuging the obtained NiCo-LDH suspension at 4000r/min for 1min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12h to obtain NiCo-LDH material; placing the obtained NiCo-LDH material into a quartz boat, placing the quartz boat into a tube furnace, introducing air as a calcining atmosphere, heating to 250 ℃ at 3 ℃/min, calcining for 2 hours at 250 ℃, cooling to normal temperature, and taking out the quartz boat to finally obtain the MOFs-derived nano-sheet self-assembled graded double-layer hollow nano-rod material (marked as 1#NiCoO material) which is a black solid. The prepared 1#NiCoO material can be directly applied to photocatalysis of CO 2 And (5) reduction.
Fig. 1 is an SEM image of the Co precursor obtained in this example, and it can be seen from fig. 1 that the material has a moderate aspect ratio.
FIG. 2 is an SEM image of a Co-ZIF material obtained in the example, and it can be seen from FIG. 2 that the structural unit of the material is relatively moderate.
Fig. 3 is an SEM image of the 1# nicoo material obtained in this example, and it can be seen from fig. 3 that the material has abundant two-dimensional nanoplatelets, and at the same time, an internal porous hollow structure can be observed through the pores.
Fig. 4 is a TEM image of the 1# nicoo material obtained in this example, and the apparent double-layer hollow structure is seen from fig. 4, and has an apparent nano-sheet structure.
FIG. 5 is a PXRD spectrum of the 1#NiCoO material obtained in this example, and as can be seen from FIG. 5, the PXRD peaks of 1#NiCoO are at 36.7 °, 44.6 ° and 65 °, corresponding to NiCo 2 O 4 Is a diffraction peak of (2).
Example 2
The embodiment provides a preparation method of MOFs derived nano-sheet self-assembly hierarchical double-layer hollow nano-rod material, which comprises the following steps:
(1) 0.5g Co (C) 2 H 3 O 2 ) 2 Adding 0.5g of surfactant into 200mL of ethanol, and performing ultrasonic dispersion for 5min to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) at 85 ℃ for 2 hours to obtain Co precursor suspension, centrifugally separating the obtained Co precursor suspension, fully washing with ethanol, and finally drying in a 60 ℃ oven for 12 hours to obtain a Co precursor material;
(3) Weighing 20mg of the Co precursor obtained in the step (2), dispersing into 10mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain pink suspension A; adding 4.0g of organic ligand into 150mL of ethanol for dissolution to obtain colorless transparent solution B; mixing the suspension A with the solution B, heating at 110 ℃ for 2 hours to obtain Co-ZIF suspension, centrifuging the obtained Co-ZIF suspension for 1min at 4000r/min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12 hours to obtain a Co-ZIF material;
(4) Weighing 40mg of the Co-ZIF material obtained in the step (3), dispersing the Co-ZIF material into 80mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain a suspension C; 91mgNi (NO) 3 ) 2 ·6H 2 O is dissolved in 10mL of water to obtain solution D; mixing the suspension C with the solution D, heating at 85 ℃ for 5min to obtain NiCo-LDH suspension, centrifuging the obtained NiCo-LDH suspension at 4000r/min for 1min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12h to obtain NiCo-LDH material; placing the obtained NiCo-LDH material into a quartz boat, placing the quartz boat into a tube furnace, introducing air as a calcining atmosphere, heating to 250 ℃ at 3 ℃/min, calcining for 2 hours at 250 ℃, cooling to normal temperature, and taking out the quartz boat to finally obtain the MOFs-derived nano-sheet self-assembled graded double-layer hollow nano-rod material (marked as 2#NiCoO material) which is a black solid. The prepared 2#NiCoO material can be directly applied to photocatalysis of CO 2 And (5) reduction.
FIG. 5 is a PXRD spectrum of the 2#NiCoO material obtained in this example, and as can be seen from FIG. 5, the PXRD peaks of the 2#NiCoO are at 36.7 °, 44.6 ° and 65 °, corresponding to NiCo 2 O 4 Is a diffraction peak of (2).
Example 3
The embodiment provides a preparation method of MOFs derived nano-sheet self-assembly hierarchical double-layer hollow nano-rod material, which comprises the following steps:
(1) 0.5g Co (C) 2 H 3 O 2 ) 2 Adding 0.5g of surfactant into 200mL of ethanol, and performing ultrasonic dispersion for 5min to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) at 85 ℃ for 2 hours to obtain Co precursor suspension, centrifugally separating the obtained Co precursor suspension, fully washing with ethanol, and finally drying in a 60 ℃ oven for 12 hours to obtain a Co precursor material;
(3) Weighing 20mg of the Co precursor obtained in the step (2), dispersing into 10mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain pink suspension A; adding 4.0g of organic ligand into 150mL of ethanol for dissolution to obtain colorless transparent solution B; mixing the suspension A with the solution B, heating at 110 ℃ for 2 hours to obtain Co-ZIF suspension, centrifuging the obtained Co-ZIF suspension for 1min at 4000r/min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12 hours to obtain a Co-ZIF material;
(4) Weighing 40mg of the Co-ZIF material obtained in the step (3), dispersing the Co-ZIF material into 80mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain a suspension C; heating the suspension C at 85 ℃ for 20min to obtain Co-OH suspension, centrifuging the obtained Co-OH suspension at 4000r/min for 1min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12h to obtain Co-OH material; placing the obtained Co-OH material into a quartz boat, placing the quartz boat into a tube furnace, introducing air as a calcining atmosphere, heating to 250 ℃ at 3 ℃/min, calcining for 2 hours at 250 ℃, cooling to normal temperature, and taking out the quartz boat to finally obtain the MOFs-derived nano-sheet self-assembled graded double-layer hollow nano-rod material (marked as 3#NiCoO material) which is a black solid. The prepared 3#NiCoO material can be directly applied to photocatalysis of CO 2 And (5) reduction.
FIG. 5 is a PXRD spectrum of the 3#NiCoO material obtained in this example, and as can be seen from FIG. 5, the PXRD peaks of 3#NiCoO are at 36.8 °, 59 ° and 65 °, corresponding to Co 3 O 4 Is a diffraction peak of (2).
Example 4
The embodiment provides a preparation method of MOFs derived nano-sheet self-assembly hierarchical double-layer hollow nano-rod material, which comprises the following steps:
(1) 0.1g Co (C) 2 H 3 O 2 ) 2 And 0.6g of surfactant are added into 200mL of ethanol, and ultrasonic dispersion is carried out for 5min to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) at 85 ℃ for 2 hours to obtain Co precursor suspension, centrifugally separating the obtained Co precursor suspension, fully washing with ethanol, and finally drying in a 60 ℃ oven for 12 hours to obtain a Co precursor material;
(3) Weighing 20mg of the Co precursor obtained in the step (2), dispersing into 10mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain pink suspension A; adding 4.0g of organic ligand into 150mL of ethanol for dissolution to obtain colorless transparent solution B; mixing the suspension A with the solution B, heating at 110 ℃ for 2 hours to obtain Co-ZIF suspension, centrifuging the obtained Co-ZIF suspension for 1min at 4000r/min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12 hours to obtain a Co-ZIF material;
(4) Weighing 40mg of the Co-ZIF material obtained in the step (3), dispersing the Co-ZIF material into 80mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain a suspension C; 182mgNi (NO) 3 ) 2 ·6H 2 O is dissolved in 10mL of water to obtain solution D; mixing the suspension C with the solution D, heating at 85 ℃ for 5min to obtain NiCo-LDH suspension, centrifuging the obtained NiCo-LDH suspension at 4000r/min for 1min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12h to obtain NiCo-LDH material; placing the obtained NiCo-LDH material into a quartz boat, placing the quartz boat into a tube furnace, introducing air as a calcining atmosphere, heating to 250 ℃ at 3 ℃/min, calcining for 2 hours at 250 ℃, cooling to normal temperature, and taking out the quartz boat to finally obtain the MOFs-derived nano-sheet self-assembled graded double-layer hollow nano-rod material (marked as 4#NiCoO material) which is a black solid. The prepared 4#NiCoO material can be directly applied to photocatalysis of CO 2 And (5) reduction.
Fig. 6 is an SEM image of the Co precursor material obtained in this example, and it can be observed that the rod-like structure of the material has a larger aspect ratio.
Example 5
The embodiment provides a preparation method of MOFs derived nano-sheet self-assembly hierarchical double-layer hollow nano-rod material, which comprises the following steps:
(1) 0.5g Co (C) 2 H 3 O 2 ) 2 Adding 0.1g of surfactant into 200mL of ethanol, and performing ultrasonic dispersion for 5min to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) at 85 ℃ for 2 hours to obtain Co precursor suspension, centrifugally separating the obtained Co precursor suspension, fully washing with ethanol, and finally drying in a 60 ℃ oven for 12 hours to obtain a Co precursor material;
(3) Weighing 20mg of the Co precursor obtained in the step (2), dispersing into 10mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain pink suspension A; adding 4.0g of organic ligand into 150mL of ethanol for dissolution to obtain colorless transparent solution B; mixing the suspension A with the solution B, heating at 110 ℃ for 2 hours to obtain Co-ZIF suspension, centrifuging the obtained Co-ZIF suspension for 1min at 4000r/min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12 hours to obtain a Co-ZIF material;
(4) Weighing 40mg of the Co-ZIF material obtained in the step (3), dispersing the Co-ZIF material into 80mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain a suspension C; 182mgNi (NO) 3 ) 2 ·6H 2 O is dissolved in 10mL of water to obtain solution D; mixing the suspension C with the solution D, heating at 85 ℃ for 5min to obtain NiCo-LDH suspension, centrifuging the obtained NiCo-LDH suspension at 4000r/min for 1min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12h to obtain NiCo-LDH material; placing the obtained NiCo-LDH material into a quartz boat, placing the quartz boat into a tube furnace, introducing air as a calcining atmosphere, heating to 250 ℃ at 3 ℃/min, calcining for 2 hours at 250 ℃, cooling to normal temperature, and taking out the quartz boat to finally obtain the MOFs-derived nano-sheet self-assembled graded double-layer hollow nano-rod material (marked as 5#NiCoO material) which is a black solid. The prepared 5#NiCoO material can be directly applied to photocatalysis of CO 2 And (5) reduction.
Fig. 7 is an SEM image of the Co precursor material obtained in this example, and it can be observed that the rod-like structure of the material has a small aspect ratio.
Example 6
The embodiment provides a preparation method of MOFs derived nano-sheet self-assembly hierarchical double-layer hollow nano-rod material, which comprises the following steps:
(1) 0.5g Co (C) 2 H 3 O 2 ) 2 Adding 0.5g of surfactant into 200mL of ethanol, and performing ultrasonic dispersion for 5min to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) at 85 ℃ for 2 hours to obtain Co precursor suspension, centrifugally separating the obtained Co precursor suspension, fully washing with ethanol, and finally drying in a 60 ℃ oven for 12 hours to obtain a Co precursor material;
(3) Weighing 20mg of the Co precursor obtained in the step (2), dispersing into 10mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain pink suspension A; adding 2.5g of organic ligand into 150mL of ethanol for dissolution to obtain colorless transparent solution B; mixing the suspension A with the solution B, heating at 110 ℃ for 2 hours to obtain Co-ZIF suspension, centrifuging the obtained Co-ZIF suspension for 1min at 4000r/min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12 hours to obtain a Co-ZIF material;
(4) Weighing 40mg of the Co-ZIF material obtained in the step (3), dispersing the Co-ZIF material into 80mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain a suspension C; 182mgNi (NO) 3 ) 2 ·6H 2 O is dissolved in 10mL of water to obtain solution D; mixing the suspension C with the solution D, heating at 85 ℃ for 5min to obtain NiCo-LDH suspension, centrifuging the obtained NiCo-LDH suspension at 4000r/min for 1min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12h to obtain NiCo-LDH material; placing the obtained NiCo-LDH material into a quartz boat, placing the quartz boat into a tube furnace, introducing air as a calcining atmosphere, heating to 250 ℃ at 3 ℃/min, calcining for 2 hours at 250 ℃, cooling to normal temperature, and taking out the quartz boat to finally obtain the MOFs-derived nano-sheet self-assembled graded double-layer hollow nano-rod material (marked as 6#NiCoO material) which is a black solid. The prepared 6#NiCoO material can be directly applied to photocatalysis of CO 2 And (5) reduction.
FIG. 8 is an SEM image of a Co-ZIF material obtained in this example, and it is observed that the structural units of the material are relatively open.
Example 7
The embodiment provides a preparation method of MOFs derived nano-sheet self-assembly hierarchical double-layer hollow nano-rod material, which comprises the following steps:
(1) 0.5g Co (C) 2 H 3 O 2 ) 2 Adding 0.5g of surfactant into 200mL of ethanol, and performing ultrasonic dispersion for 5min to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) at 85 ℃ for 2 hours to obtain Co precursor suspension, centrifuging the obtained Co precursor suspension for 1min at 3000r/min, taking the precipitate, fully washing the precipitate with ethanol, and drying at 60 ℃ for 12 hours to obtain a Co precursor material;
(3) Weighing 20mg of the Co precursor obtained in the step (2), dispersing into 10mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain pink suspension A; adding 10.0g of organic ligand into 150mL of ethanol for dissolution to obtain colorless transparent solution B; mixing the suspension A with the solution B, heating at 110 ℃ for 2 hours to obtain Co-ZIF suspension, centrifuging the obtained Co-ZIF suspension for 1min at 4000r/min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12 hours to obtain a Co-ZIF material;
(4) Weighing 40mg of the Co-ZIF material obtained in the step (3), dispersing the Co-ZIF material into 80mL of ethanol, and carrying out ultrasonic treatment for 3min to obtain a suspension C; 182mgNi (NO) 3 ) 2 ·6H 2 O is dissolved in 10mL of water to obtain solution D; mixing the suspension C with the solution D, heating at 85 ℃ for 5min to obtain NiCo-LDH suspension, centrifuging the obtained NiCo-LDH suspension at 4000r/min for 1min, taking the precipitate, fully washing with ethanol, and drying at 60 ℃ for 12h to obtain NiCo-LDH material; placing the obtained NiCo-LDH material into a quartz boat, placing the quartz boat into a tube furnace, introducing air as a calcining atmosphere, heating to 250 ℃ at 3 ℃/min, calcining for 2 hours at 250 ℃, cooling to normal temperature, and taking out the quartz boat to finally obtain the MOFs-derived nano-sheet self-assembled graded double-layer hollow nano-rod material (marked as 7#NiCoO material) which is a black solid. The prepared 7#NiCoO material can be directly applied to photocatalysis of CO 2 And (5) reduction.
FIG. 9 is an SEM image of a Co-ZIF material obtained in this example, and it was observed that the structural units of the material were too much compared.
Example 8
Nanosheet self-assembled hierarchical double-layer hollow nanorod material photocatalytic CO 2 Reduction performanceTesting
In a quartz bottle, 0.5mg of the catalyst (1#NiCoO material prepared in example 1 or 3#NiCoO material prepared in example 3) was added, respectively, followed by 4mL of water, 2mL of triethanolamine and 9mL of acetonitrile, and then 25mg of tris (2, 2-bipyridine) chloride hexahydrate was weighed. Sealing and vacuumizing quartz bottle, and injecting diluted CO 2 Gas (CO) 2 Ar=1:9) to normal pressure, reacting under the irradiation of a xenon lamp, and taking a gas product in the reaction process to obtain real-time gas (CO and H) by adopting gas chromatography analysis 2 ) Yield.
FIG. 10 is a schematic illustration of photocatalytic CO using the 1#NiCoO material used in this example 2 Reduction reaction performance test results. FIG. 10 shows that the material has high catalytic activity and good CO selectivity. The gas yield is approximately 350mmol/g for 3h, the CO selectivity is up to 91%, and the self-assembled double-layer hollow structure of the nano-sheet is proved to be used for photocatalysis of CO 2 The advantage in the reduction reaction is that the material photocatalytic CO can be obviously improved after the nickel ions are introduced 2 The CO product selectivity of the reduction reaction.
FIG. 11 is a 3#NiCoO material photocatalytic CO used in this example 2 Reduction reaction performance test results. FIG. 11 shows that the material has good photocatalytic CO 2 The reduction activity proves that the self-assembled double-layer hollow structure of the nano sheet catalyzes CO in the photocatalysis 2 Advantages in the reduction reaction.
The above examples are only preferred embodiments of the present invention, and are merely for illustrating the present invention, not for limiting the present invention, and those skilled in the art should not be able to make any changes, substitutions, modifications and the like without departing from the spirit of the present invention.
Claims (8)
1. The preparation method of the MOFs derived nano-sheet self-assembly grading double-layer hollow nano-rod material is characterized by comprising the following steps of:
(1) Co (C) 2 H 3 O 2 ) 2 And a surfactant are dissolved in ethanol to obtain a mixed solution;
(2) Heating and stirring the mixed solution obtained in the step (1), and centrifugally drying to obtain a Co precursor;
(3) Adding the Co precursor in the step (2) into ethanol, and uniformly dispersing by ultrasonic waves to obtain a suspension A; dispersing an organic ligand in ethanol to obtain a solution B; mixing the suspension A with the solution B, heating, stirring, centrifuging and drying to obtain a Co-ZIF material;
(4) Adding ethanol into the Co-ZIF material obtained in the step (3), and uniformly dispersing by ultrasonic to obtain a suspension C; ni (NO) 3 ) 2 ·6H 2 O is dissolved in water to obtain solution D; mixing the suspension C with the solution D, heating, stirring, centrifugally drying, and calcining to obtain the MOFs-derived nanosheet self-assembled hierarchical double-layer hollow NiCoO nanorod material;
in the step (1), the surfactant is polyvinylpyrrolidone, and Co (C) 2 H 3 O 2 ) 2 The mass ratio of the surfactant to the surfactant is 1:6-5:1;
in the step (3), the organic ligand is 2-methylimidazole, and the concentration of the organic ligand is 0.2-0.8mol/L.
2. The method for preparing the MOFs-derived nano-sheet self-assembled hierarchical double-layer hollow nano-rod material according to claim 1, wherein in the step (2), the temperature of heating and stirring is 60-110 ℃, and the time of heating and stirring is 1-2h.
3. The method for preparing the MOFs-derived nano-sheet self-assembled hierarchical double-layer hollow nano-rod material according to claim 1, wherein in the step (3), the concentration of the suspension a is 2-8g/L.
4. The method for preparing the MOFs-derived nano-sheet self-assembled hierarchical double-layer hollow nano-rod material according to claim 1, wherein in the step (3), the temperature of heating and stirring is 80-120 ℃, and the time of heating and stirring is 2-4h.
5. The method for preparing the MOFs-derived nano-sheet self-assembled hierarchical double-layer hollow nano-rod material according to claim 1, wherein in the step (4), the concentration of the suspension C is 0.2-0.6 g/L; the concentration of the solution D is 0-0.1mol/L.
6. The method for preparing the MOFs-derived nano-sheet self-assembled graded double-layer hollow nano-rod material according to claim 1, wherein in the step (4), the heating temperature is 80-90 ℃, and the heating time is 5-20min.
7. The method for preparing the MOFs-derived nano-sheet self-assembled hierarchical double-layer hollow nano-rod material according to claim 1, wherein in the step (4), the calcination treatment adopts an air atmosphere; the temperature of the calcination treatment is 200-450 ℃, the time of the calcination treatment is 2-3 h, and the temperature rising rate is 3-5 ℃ per minute.
8. A MOFs-derived nanoplatelet self-assembled graded bilayer hollow nanorod material prepared by the preparation method of any one of claims 1 to 7.
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