CN117166000A - Preparation method and application of bismuth-based metal organic framework material - Google Patents
Preparation method and application of bismuth-based metal organic framework material Download PDFInfo
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- CN117166000A CN117166000A CN202311060151.1A CN202311060151A CN117166000A CN 117166000 A CN117166000 A CN 117166000A CN 202311060151 A CN202311060151 A CN 202311060151A CN 117166000 A CN117166000 A CN 117166000A
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- 239000000463 material Substances 0.000 title claims abstract description 130
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 122
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 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 18
- 235000019253 formic acid Nutrition 0.000 claims abstract description 18
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001621 bismuth Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 abstract description 22
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 35
- 238000002441 X-ray diffraction Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 230000035484 reaction time Effects 0.000 description 18
- 239000012265 solid product Substances 0.000 description 18
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- 238000001035 drying Methods 0.000 description 17
- 239000005457 ice water Substances 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZZHAYFWMLLWGG-UHFFFAOYSA-K triazanium;bismuth;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].[NH4+].[NH4+].[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VZZHAYFWMLLWGG-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of electrocatalysts, and discloses a preparation method and application of a bismuth-based metal organic framework material. The method comprises the following steps: dispersing bismuth salt and 1,3, 5-trimesic acid in an organic solvent, carrying out ultrasonic treatment, and obtaining a bismuth-based metal organic frame material CAU-17 by utilizing cavitation of ultrasonic waves; bismuth salt is bismuth nitrate; the organic solvent is methanol or absolute ethanol. The bismuth-based metal organic framework material is a cylindrical short rod, has uniform crystal size, uniform bismuth element distribution and high relative content, and is used for CO 2 The electro-reduction system can show excellent Faraday efficiency of formic acid, and shows excellent electro-catalytic CO in long-time catalytic reaction 2 Reduced formic acid producing PropertyAnd good stability, easy realization of mass preparation and wide application prospect. The bismuth-based metal organic framework material is used for preparing an electrocatalytic reduction carbon dioxide catalyst.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a preparation method and application of a bismuth-based metal organic framework material CAU-17.
Background
CO 2 Is the highest oxidation state of carbon, is in a linear structure and has very low Gibbs free energy (-394.4 kJ.mol) -1 ) The carbon-carbon double bond is short in length and high in energy, and is a molecule with high thermodynamic stability and chemical inertness. Therefore, it is desired to realize efficient CO 2 Electro-reduction, a suitable catalyst is required to reduce the activation energy required for the reaction and to increase the reaction rate. Metal Organic Frameworks (MOFs) as a CO 2 The electro-reduction catalyst has atomic-level dispersed active sites, large specific surface area and controllable chemical adjustability, is widely concerned and reported, and is a CO with great potential 2 An electro-reduction catalyst. However, most of the MOFs reported at present are prepared by a solvothermal method, and have the problems of long synthesis period, high energy consumption, high production cost, poor repeatability, generation of toxic and harmful waste liquid, certain dangers and the like, so that the MOFs are not beneficial to large-scale industrial production and application. And the catalytic performance of the metal organic frameworks prepared by the existing method is also to be improved.
Therefore, the electrocatalytic reduction CO with excellent catalytic performance, low price, simple preparation process and safe and environment-friendly preparation process is developed 2 The catalyst has very important significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a bismuth-based metal organic framework material CAU-17.
The technical scheme adopted by the invention is as follows:
a method for preparing bismuth-based metal organic framework material (CAU-17), comprising the steps of: dispersing bismuth salt and 1,3, 5-trimesic acid in an organic solvent, carrying out ultrasonic treatment, and obtaining the bismuth-based metal organic frame material (CAU-17) by utilizing cavitation of ultrasonic waves.
Preferably, the molar ratio of the bismuth salt to the 1,3, 5-trimesic acid is 0.01-0.1:1.
Preferably, the bismuth salt is bismuth nitrate.
Preferably, the organic solvent is methanol or absolute ethanol.
Further preferably, the organic solvent is methanol.
Preferably, the conditions of the ultrasonic treatment are as follows: the ultrasonic power is more than 10W; ultrasonic duty cycle: 50%; ultrasonic time: 2-20 min.
Further preferably, the ultrasonic power is 100 to 700W.
A bismuth-based metal organic framework material (CAU-17) made by the above-described method of preparation.
An electrocatalytic reduction carbon dioxide catalyst comprising the bismuth-based metal organic framework material (CAU-17) described above.
The beneficial effects of the invention are as follows: the bismuth-based metal organic framework material (CAU-17) is a cylindrical short rod, has uniform dimension, uniform distribution of bismuth elements and high relative content, and is used for CO 2 The electric reduction system can show excellent formic acid Faraday efficiency, and the preparation method has the advantages of rapidness, simplicity, easiness in implementation, wide raw material sources, low price, low requirements on equipment, controllable preparation process, environmental friendliness and the like, is easy to realize mass preparation, and has wide application prospect.
Specifically:
1) The bismuth-based metal organic framework material (CAU-17) is a cylindrical short rod, and the crystal size is uniform;
2) The bismuth-based metal organic framework material (CAU-17) has uniform distribution of bismuth element and high relative content (Bi is 44.6 percent relative mass percent) and is used for CO 2 The electric reduction system can show excellent Faraday efficiency of formic acid, the Faraday efficiency of formic acid is excellent under the potential of-1.0 to-1.5V vs RHE, and the highest Faraday efficiency can reach 99%;
3) The preparation method of the bismuth-based metal organic framework material (CAU-17) is quick, simple and green, wide in raw material source, low in price, low in equipment requirement, controllable in preparation process, environment-friendly, easy to realize mass preparation and wide in application prospect.
Drawings
FIG. 1 is an XRD pattern of bismuth-based metal organic framework material (CAU-17) in examples 1 to 4 and comparative example 1;
FIG. 2 is an XRD pattern of bismuth-based metal organic framework material (CAU-17) in examples 5 to 8;
FIG. 3 is an XRD pattern of bismuth-based metal organic framework material (CAU-17) in examples 9 to 11;
FIG. 4 is an SEM image of bismuth-based metal-organic framework material (CAU-17) of examples 9 and 10;
FIG. 5 is a TEM image and elemental distribution diagram of bismuth-based metal-organic framework material (CAU-17) in example 10;
FIG. 6 is an XRD pattern of the bismuth-based material of comparative example 2;
FIG. 7 is an XRD pattern of the bismuth-based material of comparative example 3;
FIG. 8 is an XRD pattern of bismuth-based materials in comparative examples 4 to 7;
FIG. 9 shows the electrocatalytic reduction of CO at different potentials for the bismuth-based metal organic framework material (CAU-17) in examples 4, 9 and 10 2 LSV, faraday efficiency of each product and formic acid yield plot;
FIG. 10 shows the electrocatalytic reduction of CO at different potentials for bismuth-based metal organic framework material (CAU-17) in example 10 and comparative example 7 2 LSV, faraday efficiency of each product and formic acid yield plot;
FIG. 11 is a graph of the stability test of bismuth-based metal organic framework material (CAU-17) at-1.2V vs. RHE in example 10.
Detailed Description
The invention is further illustrated and described below in connection with specific examples, but embodiments of the invention are not limited thereto.
Example 1:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to be 100W, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic completion, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 1.
As can be seen from fig. 1: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 1 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Example 2:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL methanol, placing in an ice-water bath, reacting by using an ultrasonic cell grinder, setting the ultrasonic power to 300W, setting the total ultrasonic reaction time to 10min, setting the ultrasonic mode to ultrasonic for 3s, spacing for 3s, carrying out suction filtration after ultrasonic finishing, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 1.
As can be seen from fig. 1: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 2 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Example 3:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to be 500W, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic completion, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 1.
As can be seen from fig. 1: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 3 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Example 4:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to 700W, setting the total ultrasonic reaction time to 10min, setting the ultrasonic mode to ultrasonic for 3s at intervals of 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 1.
As can be seen from fig. 1: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 4 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Example 5:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL ethanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to be 100W, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 2.
As can be seen from fig. 2: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 5 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Example 6:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL ethanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to 300W, setting the total ultrasonic reaction time to 10min, setting the ultrasonic mode to ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 2.
As can be seen from fig. 2: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 6 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Example 7:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL ethanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to be 500W, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 2.
As can be seen from fig. 2: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 7 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Example 8:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL ethanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to 700W, setting the total ultrasonic reaction time to 10min, setting the ultrasonic mode to ultrasonic for 3s at intervals of 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 2.
As can be seen from fig. 2: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 8 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Example 9:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to 700W, setting the total ultrasonic reaction time to 5min, setting the ultrasonic mode to ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 3, and the SEM is shown in FIG. 4.
As can be seen from fig. 3: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 9 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
As can be seen from fig. 4: the bismuth-based metal organic framework material (CAU-17) in the embodiment has good crystallization performance and uniform crystal size, and presents the appearance of a cylindrical short bar.
Example 10:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to 700W, setting the total ultrasonic reaction time to 2min, setting the ultrasonic mode to ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 3, the SEM is shown in FIG. 4, and the TEM and element distribution pattern is shown in FIG. 5.
As can be seen from fig. 3: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 10 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
As can be seen from fig. 4: the bismuth-based metal organic framework material (CAU-17) in the embodiment has good crystallization performance and uniform crystal size, and presents the appearance of a cylindrical short bar.
As can be seen from fig. 5: the bismuth-based metal organic framework material (CAU-17) prepared in this example has a uniform distribution of C, O, bi elements.
The mass fraction of Bi element in the sample prepared in test example 11 was 44.6% by ICP-OES.
Example 11:
bismuth-based metal organic framework material (CAU-17) prepared by the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL ethanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to 700W, setting the total ultrasonic reaction time to 2min, setting the ultrasonic mode to ultrasonic for 3s at intervals of 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based metal organic frame material (CAU-17) (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based metal organic framework material (CAU-17) in this example is shown in FIG. 3.
As can be seen from fig. 3: the diffraction peak positions of the bismuth-based metal organic framework material (CAU-17) in this example were consistent with that of single crystal simulated CAU-17, indicating that the conditions of example 11 were able to successfully produce a material with typical CAU-17 with ultrasonic assistance.
Comparative example 1:
a bismuth-based material, the preparation of which comprises the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to be 10W, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic treatment, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain bismuth-based material (white powder).
The X-ray diffraction (XRD) pattern of the bismuth-based material in this comparative example is shown in fig. 1.
As can be seen from fig. 1: the diffraction peak position of the bismuth-based material in the embodiment is compared with that of the single crystal simulated CAU-17, and the characteristic three strong peaks of the typical CAU-17 almost disappear in a scanning angle of 5-10 degrees, which shows that the CAU-17 material cannot be prepared with low ultrasonic power (below 10W) under the assistance of ultrasonic waves.
Comparative example 2:
a bismuth-based material, the preparation of which comprises the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL n-propanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to be 700W, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, carrying out suction filtration after ultrasonic completion, and drying the filtered solid product in a vacuum oven at 60 ℃ for 6h to obtain bismuth-based material (white powder).
The XRD patterns of the bismuth-based material in this comparative example are shown in FIG. 6.
As can be seen from fig. 6: the diffraction peaks of the bismuth-based material in this comparative example were not consistent with that of the single crystal simulated CAU-17, indicating that CAU-17 could not be prepared under the conditions of comparative example 2 when n-propanol was used as the solvent.
Comparative example 3:
a bismuth-based material, the preparation of which comprises the steps of:
dispersing 0.150g (0.309 mmol) bismuth nitrate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL deionized water, placing in an ice-water bath, reacting by using an ultrasonic cell grinder, setting ultrasonic powers to be 700W, 800W, 900W and 990W respectively, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, spacing for 3s, carrying out suction filtration after ultrasonic finishing, and drying the solid product obtained by filtration in a vacuum oven at 60 ℃ for 6h to obtain the bismuth-based material (white powder).
The XRD patterns of the bismuth-based material in this comparative example are shown in FIG. 7.
As can be seen from fig. 7: the diffraction peaks of the bismuth-based material in this comparative example were not consistent with that of the single crystal simulated CAU-17, indicating that CAU-17 could not be prepared under the conditions of comparative example 3 with deionized water as the solvent.
Comparative example 4:
a bismuth-based material, the preparation of which comprises the steps of:
dispersing 0.140g (0.309 mmol) of bismuth ammonium citrate and 0.750g (3.569 mmol) of 1,3, 5-trimesic acid in 30mL of methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to be 700W, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, carrying out suction filtration after the ultrasonic is finished, and drying the filtered solid product in a vacuum oven at 60 ℃ for 6h to obtain bismuth-based material (white powder).
The XRD patterns of the bismuth-based material in this comparative example are shown in FIG. 8.
As can be seen from fig. 8: the diffraction peaks of the bismuth-based material in this comparative example were not consistent with that of the single crystal simulated CAU-17, indicating that CAU-17 could not be prepared under the conditions of comparative example 4 when bismuth ammonium citrate was used as the bismuth source.
Comparative example 5:
a bismuth-based material, the preparation of which comprises the steps of:
dispersing 0.098g (0.309 mmol) of sodium bismuthate and 0.750g (3.569 mmol) of 1,3, 5-trimesic acid in 30mL of methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to be 700W, setting the total ultrasonic reaction time to be 10min, setting the ultrasonic mode to be ultrasonic for 3s, carrying out suction filtration after the ultrasonic is finished, and drying the filtered solid product in a vacuum oven at 60 ℃ for 6h to obtain bismuth-based material (white powder).
The XRD patterns of the bismuth-based material in this comparative example are shown in FIG. 8.
As can be seen from fig. 8: the diffraction peaks of the bismuth-based material in this comparative example were not consistent with that of the single crystal simulated CAU-17, indicating that CAU-17 could not be prepared under the conditions of comparative example 5 when sodium bismuthate was used as the bismuth source.
Comparative example 6:
a bismuth-based material, the preparation of which comprises the steps of:
dispersing 0.228g (0.309 mmol) bismuth sulfate and 0.750g (3.569 mmol) 1,3, 5-trimesic acid in 30mL methanol, placing in an ice-water bath, performing reaction by using an ultrasonic cell grinder, setting the ultrasonic power to 700W, setting the total ultrasonic reaction time to 10min, setting the ultrasonic mode to ultrasonic for 3s, spacing for 3s, performing suction filtration after ultrasonic completion, and drying the obtained solid product in a vacuum oven at 60 ℃ for 6h to obtain bismuth-based material (white powder).
The XRD patterns of the bismuth-based material in this comparative example are shown in FIG. 8.
As can be seen from fig. 8: the diffraction peaks of the bismuth-based material in this comparative example were not consistent with that of the single crystal simulated CAU-17, indicating that CAU-17 could not be prepared under the conditions of comparative example 6 when bismuth sulfate was used as the bismuth source.
Comparative example 7:
a bismuth-based metal organic framework material (CAU-17) prepared by microwave method comprising the steps of:
bismuth nitrate (0.375 g, 773 mmol) and trimesic acid (0.750 g, 3.569 mmol) are dispersed in 30mL of methanol, a microwave reactor is utilized for reaction, the constant temperature is set to be 66 ℃, the total reaction time is 10min, suction filtration is carried out, and the filtered solid product is placed in a vacuum oven and dried for 6h at 60 ℃, thus obtaining the bismuth-based metal organic frame material (white powder).
The XRD patterns of the bismuth-based metal-organic framework materials in this comparative example are shown in FIG. 8.
As can be seen from fig. 8: the diffraction peak position of the bismuth-based metal organic framework material (CAU-17) in this comparative example was consistent with that of the single crystal simulated CAU-17, indicating that the conditions of comparative example 7 were able to successfully produce a material with typical CAU-17 with the aid of microwaves.
Electrocatalytic performance test:
5mg of bismuth-based metal organic frame material (CAU-17) in examples 4, 9, 10 and comparative example 7 were weighed respectively to prepare catalyst ink, which was then coated on hydrophobic carbon paper, dried, and used as a working electrode, a platinum sheet as a counter electrode, an Ag/AgCl electrode as a reference electrode (for convenience of comparison, electrode potential was converted into reversible hydrogen electrode), KHCO with a concentration of 0.1mol/L 3 Solution (CO) 2 Saturated) as electrolyte, CO in an H-cell 2 And (5) electric reduction testing. Examples 4, 9 and 10 electrocatalytic CO at different potentials of bismuth-based Metal organic framework Material (CAU-17) 2 The performance of the reduction and the formic acid production rate are shown in FIG. 9. Will be solidExample 10 and comparative example 7 bismuth-based organic frame Material (CAU-17) prepared by electrocatalytic CO 2 Reduction reaction to obtain electrocatalytic CO under different potentials 2 The current density of the reduction, the formic acid production performance and the formic acid production rate are shown in FIG. 10. The bismuth-based metal organic framework material (CAU-17) prepared in example 10 was applied to long-term electrocatalytic CO at an optimal test potential of-1.2V vs. RHE 2 The reduction reaction is shown in FIG. 11.
As can be seen from fig. 9: for the bismuth-based metal organic framework material (CAU-17) in examples 4, 9 and 10, excellent electrocatalytic CO was exhibited over a wide potential range of-1.0 to-1.5V vs. RHE 2 The performance of reducing and producing formic acid can reach 99% of the optimal Faraday efficiency of formic acid, and the yield of formic acid is higher as the potential is more negative.
As can be seen from fig. 10: as can be seen from the LSV curve, the saturated CO of example 10 after the initial potential 2 Current density and saturation N under atmosphere 2 The difference in current density under atmosphere is greater than that of saturated CO of comparative example 7 2 Current density and saturation N under atmosphere 2 The difference of current density under the atmosphere initially shows that the CAU-17 prepared by the ultrasonic method has more excellent electrocatalytic CO 2 Reduction performance; further, by electrocatalytic CO at constant potential 2 Reduction performance test shows that CAU-17 prepared in example 10 electrocatalytic CO at a broad potential (-1.0 to-1.5V vs. RHE) 2 Faraday efficiency and yield of reduced formic acid are better than those of CAU-17 electrocatalytic CO prepared in comparative example 7 2 The Faraday efficiency and yield of the reduced formic acid show that the prepared CAU-17 has better catalytic performance under the assistance of ultrasound.
As can be seen from fig. 11: throughout the process, CO and H 2 The average Faraday efficiencies of (a) are kept at a low level, respectively 3.18% and 4.27%, and the average Faraday efficiency of the formic acid product is 95.7%, and the average yield of the formic acid is 235.2 mu mol.h as tested by high performance liquid chromatography -1 ·cm -2 。
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a bismuth-based metal organic framework material is characterized by comprising the following steps of: the method comprises the following steps: dispersing bismuth salt and 1,3, 5-trimesic acid in an organic solvent, carrying out ultrasonic treatment, and obtaining a bismuth-based metal organic frame material CAU-17 by utilizing cavitation of ultrasonic waves;
the bismuth salt is bismuth nitrate; the organic solvent is methanol or absolute ethanol;
the ultrasonic treatment conditions are as follows: the ultrasonic power is more than 10W; ultrasonic duty cycle: 50%; ultrasonic time: 2-20 min.
2. The method for preparing the bismuth-based metal organic framework material according to claim 1, wherein: the ultrasonic power is 100-700W.
3. The method for preparing the bismuth-based metal organic framework material according to claim 1, wherein: the organic solvent is methanol.
4. The method for preparing the bismuth-based metal organic framework material according to claim 1, wherein: the molar ratio of the bismuth salt to the 1,3, 5-trimesic acid is (0.01-0.1): 1.
5. A bismuth-based metal organic framework material obtained by the production process according to any one of claims 1 to 4.
6. An electrocatalytic reduction carbon dioxide catalyst, characterized by: a bismuth-based metal organic framework material comprising the material of claim 5.
7. Use of a bismuth-based metal organic framework material obtained by the preparation method according to any one of claims 1 to 4 for preparing formic acid by electrocatalytic reduction of carbon dioxide.
8. The use according to claim 7, characterized in that: the bismuth-based metal organic framework material is used as a catalyst.
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