CN108997587B - Metal organic framework material for hydrogen production reaction by water electrolysis and preparation method of nanosheet material thereof - Google Patents
Metal organic framework material for hydrogen production reaction by water electrolysis and preparation method of nanosheet material thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 65
- 229910001868 water Inorganic materials 0.000 title claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 49
- 239000002135 nanosheet Substances 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 29
- 239000001257 hydrogen Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002178 crystalline material Substances 0.000 claims abstract description 16
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims abstract description 15
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000013384 organic framework Substances 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
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- 239000013110 organic ligand Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 1
- 229910001429 cobalt ion Inorganic materials 0.000 abstract 1
- 229910001453 nickel ion Inorganic materials 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 description 33
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- 239000002055 nanoplate Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
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- 125000004434 sulfur atom Chemical group 0.000 description 2
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- 230000007704 transition Effects 0.000 description 2
- ZYXYMEZEZFQOAK-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)propanenitrile Chemical compound C1=CC=C2SC(CCC#N)=NC2=C1 ZYXYMEZEZFQOAK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- ATWGHWZRHOJITC-UHFFFAOYSA-N [S].C1=CC=NC=C1 Chemical compound [S].C1=CC=NC=C1 ATWGHWZRHOJITC-UHFFFAOYSA-N 0.000 description 1
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- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 description 1
- KPOBHNYTWJSVKF-UHFFFAOYSA-L cobalt(2+);diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O KPOBHNYTWJSVKF-UHFFFAOYSA-L 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PTWLOSARXIJRRJ-UHFFFAOYSA-N pyridin-1-ium-4-sulfonate Chemical compound OS(=O)(=O)C1=CC=NC=C1 PTWLOSARXIJRRJ-UHFFFAOYSA-N 0.000 description 1
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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
- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01J35/33—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a metal organic framework material for hydrogen production reaction by water electrolysis and a preparation method of a nanosheet structure of the material. Belonging to the technical field of crystalline materials. The structural formula of the material is as follows: [ Co (1,4-ndc) (Py)2S)(H2O)]n. Wherein n represents n, 1,4-ndc represents 1, 4-naphthalenedicarboxylic acid, Py2S represents monothiopyridine. The metal organic framework material is a two-dimensional network structure formed by transition metal ions, organic ligand 1, 4-naphthalene diacid and auxiliary ligand monothiopyridine through coordination bonds or intermolecular force. The transition metal ion is preferably divalent cobalt or nickel ion. The metal organic framework material has good thermal stability. The nanosheet prepared by taking the metal organic framework as the precursor has relatively excellent proton transmission and electron exchange capabilities and highly exposed catalytic active sites, so that the nanosheet has better hydrogen production performance by water electrolysis. And is also expected to be a novel efficient catalyst material for hydrogen production by water electrolysis.
Description
Technical Field
The invention designs a metal organic framework material for hydrogen production reaction by water electrolysis and a nanosheet preparation method thereof, and belongs to the technical field of metal organic framework materials and nanosheets.
Background
The water electrolysis hydrogen production technology is an effective way for obtaining green energy hydrogen energy in the future. Platinum is used as an efficient water electrolysis hydrogen production catalyst, is high in price, low in earth reserve, easy to generate a catalyst poisoning phenomenon, and not beneficial to the harmonious development of hydrogen energy and hydrogen economy, so that the exploration of an efficient non-noble metal electrocatalyst has profound significance for the regeneration and efficient reasonable utilization of hydrogen energy.
The MOF is a highly crystallized solid material formed by organic ligands and metal atom nodes through coordination bonds, and has the characteristics of adjustable structure, multiple functions, rich active sites, large specific surface area, highly regular pore channel structure and the like. However, the reported MOFs materials still have the defects of slower proton transmission and electron exchange rate caused by micron-scale size effect, insufficient exposure of catalytic active sites, poor conductivity and the like, and the preparation strategy of forming ultra-thin nanosheets by means of MOFs ultrasound can effectively solve the performance weakening caused by the defects. The two-dimensional transition metal cobalt-based organic framework material and the nanosheets thereof have low-dimensional structures, and highly exposed active sites show superior performance in the application of the catalyst for hydrogen production by water electrolysis, so that the two-dimensional transition metal cobalt-based organic framework material and the nanosheets thereof are expected to become a novel efficient catalyst material for hydrogen production by water electrolysis.
Disclosure of Invention
The invention provides a transition metal cobalt-based organic framework material constructed based on 1, 4-naphthalene diacid and monothiopyridine, a preparation method of a nanosheet thereof and application of the transition metal cobalt-based organic framework material in a catalyst for hydrogen production by electrolyzing water, aiming at various defects caused by the micron-scale size effect of the existing MOFs material. The basic unit of the metal frame structure comprises a crystallographically independent Co2+Ion, a 1,4-ndc ligand and a Py2S as an ancillary ligand. One Co2+By four oxygen atoms on two 1,4-ndc ligands, one Py2The nitrogen atoms on the S are connected to form a two-dimensional mononuclear organic framework. The compound not only has good catalytic performance for hydrogen production by electrolyzing water, but also the nano-sheet prepared by the compound as a precursor has better hydrogen evolution performance than the precursor.
A metal organic framework material for hydrogen production reaction by water electrolysis and a preparation method of a nanosheet thereof are disclosed, wherein the chemical general formula of the nanosheet is [ Co (1,4-ndc) (Py)2S)(H2O)]n(ii) a Wherein n represents an infinite natural number, 1,4-ndc represents 1, 4-naphthalenedicarboxylic acid, Py2S represents monothiopyridine. Organic ligand 1,4-ndc and auxiliary ligand Py2The chemical formula of S is respectively C12H8O4And C10H8N2S, the molecular structural formula is respectively as follows:
the crystalline material belongs to a triclinic system, the space group is P-1, and the unit cell parameters are as follows:
α＝69.163°,β＝82.97°,γ＝64.352°。
the preparation method of the transition metal cobalt-based organic framework material comprises the following steps of mixing Co (Cl) under a sealed condition4)2·6H2Adding O, 1, 4-naphthalenedicarboxylic acid and monothiopyridine into deionized water, mixing, adding sodium hydroxide to regulate the pH value of the solution to 7-8, stirring, adding the solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at the constant temperature of 120-160 ℃ for 48-96h, and cooling to room temperature at the constant speed of 2-3 ℃/h, namely electrolyzing water to prepare the metal organic framework (Co (1,4-ndc) (Py) for hydrogen production reaction2S)(H2O)]nA crystalline material.
Wherein the mol ratio of the organic ligand 1, 4-naphthalene diacid, the auxiliary ligand monothiopyridine and the cobalt perchlorate is 1:1:2-2:1:2, each 0.1mmol of the organic ligand 1, 4-naphthalene diacid corresponds to 4mL of deionized water, and the concentration of the sodium hydroxide is 0.05-0.2 mol/L.
The preparation method of the transition metal cobalt-based organic framework material and the nanosheet comprises the following steps: taking a certain mass of crystal of the cobalt-based organic framework material, adding a mixed solution of methanol and isopropanol with the volume ratio of 1:1 into a mortar, grinding for 30 minutes, carrying out ultrasonic treatment for 3-8 hours, and centrifuging to obtain the nanosheet. The thickness of the nanosheet prepared from the cobalt-based organic framework nanomaterial is 1.52 +/-0.32 nm, and the specific surface area of the nanosheet is 2.6264m2/g。
The transition metal organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nAnd the corresponding nanosheets have application prospects in the field of catalysts for hydrogen production by water electrolysis.
The room temperature referred to in the invention refers to the ambient temperature under normal pressure.
The invention relates to a crystal synthesis method, a test method and data research of a metal organic framework.
The invention relates to a research on electrochemical test analysis data of a metal organic framework.
The invention relates to a metal organic framework X-ray single crystal diffractometer test and data research.
The invention develops a 1, 4-naphthalene diacid and single sulfur pyridine transition cobalt-based metal organic framework crystal material, and experiments prove that the material and nanosheets prepared from the material as precursors have catalytic properties for hydrogen production by water electrolysis, and can be applied to the field of catalyst materials for hydrogen production by water electrolysis.
The invention further discloses a growth method of the metal organic framework crystal, which is obtained by hydrothermal culture. The crystal structure was measured using a small molecule single crystal X-ray diffractometer of Rigaku, japan, and data such as diffraction intensity and unit cell parameters were measured at 120K with a graphite monochromator, Mo K α ray with a wavelength λ of 0.071073nm, and the collected data was empirically absorption-corrected using a scanning technique, and the obtained result was analyzed by direct method using the Shelxtl-97 program and corrected by full matrix least squares. The obtained crystallographic data are shown below.
Due to the adoption of the technical scheme, the experiment has the following advantages:
(1) the synthesis method is simple, the reproducibility is good, the yield is high, the requirement on temperature is low, and the temperature of a reaction system is easy to control;
(2) the auxiliary ingredient for synthesizing the crystalline material contains sulfur atoms, and the sulfur atoms have great promotion effect on the performance of electrocatalytic HER. Therefore, the MOFs material constructed by the fluorine-containing organic ligand can show excellent conductivity and electrocatalytic HER performance of the material;
(3) the crystalline material is two-dimensional layered, a large number of exposed metal sites exist on the surface of the two-dimensional MOFs, and the existence of unsaturated sites is very important for improving the catalytic performance.
(4) The nanosheet prepared by taking the metal organic framework as the precursor has better performance of hydrogen production by water electrolysis due to the excellent proton transmission and electron exchange capacity and highly exposed catalytic active sites. As shown in fig. 7-8, the performance of the nanoplatelets is far superior to bulk materials.
Drawings
FIG. 1 shows a transition metal organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nThe coordination environment diagram of (1).
FIG. 2 shows a transition metal organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nIs a reticular structure diagram of a nano sheet prepared by a precursor.
FIG. 3 shows the resulting transition metal organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nAnd powder diffraction patterns of their nanosheets. Wherein the curve corresponding to No. 1 is a simulated X-ray diffraction pattern, and the curve corresponding to No. 2 is a transition metal organic framework material [ Co (1,4-ndc) (Py) to be tested2S)(H2O)]nX-ray diffraction pattern. Number 3 corresponds to the transition metal organic framework material [ Co (1,4-ndc) (Py) tested2S)(H2O)]nAn X-ray diffraction pattern of a nanoplate prepared for the precursor.
FIG. 4 shows a transition metal organic framework material [ Co (1,4-ndc) (Py) prepared in example 12S)(H2O)]nThe scanned image of (a).
FIG. 5 shows a transition metal organic framework material [ Co (1,4-ndc) (Py) prepared in example 12S)(H2O)]nTransmission diagram of (a).
FIG. 6 shows the resulting transition metal-organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nTransmission pattern of nanoplatelets.
FIG. 7 shows a transition metal organic framework material [ Co (1,4-ndc) (Py) prepared in example 12S)(H2O)]nAnd linear sweep cyclic voltammograms of their nanosheets. The curve corresponding to the number 1 is a transition metal organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nLinear sweep cyclic voltammogram. Number 2 corresponds to the transition metal organic framework material [ Co (1,4-ndc) (Py) tested2S)(H2O)]nLinear sweep cyclic voltammogram of nanosheets prepared for the precursor.
FIG. 8 shows a transition metal organic framework material [ Co (1,4-ndc) (Py) prepared in example 12S)(H2O)]nAnd the Tafel plot of the nanosheets thereof. The curve corresponding to the number 1 is a transition metal organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nTafel plot of (a). Number 2 corresponds to the transition metal organic framework material [ Co (1,4-ndc) (Py) tested2S)(H2O)]nTafel plot of nanosheets prepared for the precursor.
FIG. 9 shows a transition metal organic framework material [ Co (1,4-ndc) (Py) prepared in example 12S)(H2O)]nAnd alternating current impedance plot of its nanosheets. The curve corresponding to the number 1 is a transition metal organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nAc impedance plot of (1). Number 2 corresponds to the transition metal organic framework material [ Co (1,4-ndc) (Py) tested2S)(H2O)]nAlternating current impedance plot of nanoplates prepared for the precursor.
FIG. 10 shows a transition metal organic framework material [ Co (1,4-ndc) (Py) of example 72S)(H2O)]nNanosheet prepared for precursor and having current density of 10mA cm-2Stability test curves up to 36 hours.
Detailed Description
The following examples are illustrative and not intended to be limiting, and the scope of the present invention is not limited by the following examples. The starting materials of the present invention are all commercially available.
The starting materials used in the examples are all commercially available. Cobalt perchlorate hexahydrate, analytically pure, Alpha; 1, 4-naphthalene diacid, analytically pure and chemostat in Jinan; monosulfopyridine, analytically pure, and chemostat in denna; NaOH, analytically pure, and Vietnam constant;
example 1
0.2mmol of Co (Cl) under sealed conditions4)2·6H2Adding O (20mg),0.1mmol of 1, 4-naphthalenedicarboxylic acid (20mg) and 0.1mmol of monothiopyridine (18mg) into 4mL of deionized water, mixing, adding sodium hydroxide to adjust the pH value of the solution to 7, stirring, adding into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at a constant temperature of 140 ℃ for 72h, and cooling to room temperature at a constant speed of 2-3 ℃/h to obtain purple blocky crystals, namely transition metal cobalt-based organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nThe crystalline material has the structure shown in the relevant content of the attached figures 1-9.
Example 2
0.1mmol of Co (Cl) under sealed conditions4)2·6H2O (10mg), 0.1mmol1, 4-naphthalenedicarboxylic acid (20mg) and 0.1mmol monothiopyridine (18mg) are added into 4mL deionized water to be mixed, then sodium hydroxide is added into the deionized water to adjust the pH value of the solution to 7, the mixture is stirred and then added into a stainless steel reaction kettle with a polytetrafluoroethylene lining to react for 96h at the constant temperature of 140 ℃, and the temperature is reduced to the room temperature at the constant speed of 2-3 ℃/h to obtain the purpleChromophoric bulk crystal, i.e. transition metal cobalt-based organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nA crystalline material.
Example 3
0.2mmol of Co (Cl) under sealed conditions4)2·6H2O (20mg),0.1mmol 1, 4-naphthalenedicarboxylic acid (20mg) and 0.1mmol monothiopyridine (18mg) are added into 4mL deionized water to be mixed, then sodium hydroxide is added to adjust the pH value of the solution to 8, the mixture is stirred and then added into a stainless steel reaction kettle with a polytetrafluoroethylene lining to react for 96 hours at a constant temperature of 120 ℃, and the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h to obtain purple blocky crystals, namely transition metal cobalt-based organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nA crystalline material.
Example 4
0.1mmol of Co (Cl) under sealed conditions4)2·6H2O (10mg), 0.1mmol1, 4-naphthalenedicarboxylic acid (20mg) and 0.1mmol monothiopyridine (18mg) are added into 4mL deionized water to be mixed, then sodium hydroxide is added to adjust the pH value of the solution to 7, the mixture is stirred and then added into a stainless steel reaction kettle with a polytetrafluoroethylene lining to react for 72 hours at a constant temperature of 120 ℃, and the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h to obtain purple blocky crystals, namely transition metal cobalt-based organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nA crystalline material.
Example 5
0.2mmol of Co (Cl) under sealed conditions4)2·6H2O (20mg),0.1mmol 1, 4-naphthalenedicarboxylic acid (20mg) and 0.1mmol monothiopyridine (18mg) are added into 4mL deionized water to be mixed, then sodium hydroxide is added to adjust the pH value of the solution to 7, the mixture is stirred and then added into a stainless steel reaction kettle with a polytetrafluoroethylene lining to react for 60 hours at a constant temperature of 160 ℃, and the temperature is reduced to room temperature at a constant speed of 2-3 ℃/h to obtain purple blocky crystals, namely transition metal cobalt-based organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nA crystalline material.
Example 6
0.2mmol of Co (Cl) under sealed conditions4)2·6H2O (20mg),0.1mmol 1, 4-naphthalenedicarboxylic acid (20mg) and 0.1mmol monothiopyridine (18mg) are added into 4mL deionized water to be mixed, then sodium hydroxide is added to adjust the pH value of the solution to 8, the mixture is stirred and then added into a stainless steel reaction kettle with a polytetrafluoroethylene lining to react for 72 hours at the constant temperature of 140 ℃, and the temperature is reduced to room temperature at the constant speed of 2-3 ℃/h to obtain purple blocky crystals, namely transition metal cobalt-based organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nA crystalline material.
Example 7
Taking the transition metal cobalt-based organic framework material [ Co (1,4-ndc) (Py) obtained in any of examples 1 to 62S)(H2O)]nTransition metal cobalt-based organic framework material of crystalline material [ Co (1,4-ndc) (Py)2S)(H2O)]n0.2g of crystalline material, 5mL of methanol and 5mL of n-propanol are dispersed in a mortar for grinding for 30 minutes, the mixture is kept stand for 10 minutes, and supernatant fluid is taken and centrifuged to obtain the transition metal cobalt-based organic framework material [ Co (1,4-ndc) (Py)2S)(H2O)]nThe corresponding nano-sheets of the crystalline material, the results are shown in the attached figures 3 and 7-10.
Example 8
Taking 10mg of the prepared MOFs, adding 0.2mL of Nafion and 1.8mL of deionized water, carrying out ultrasonic treatment for 30min to completely disperse the obtained mixture to obtain a suspension, then using a liquid transfer gun to transfer 5 mu L of the suspension, dropwise adding the suspension to a glassy carbon electrode, drying at room temperature, and carrying out drying at 0.5M H2SO4The test was performed.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (4)
1. Metal for hydrogen production reaction by water electrolysisThe preparation method of the organic framework material is characterized in that the chemical formula of the metal organic framework material is [ Co (1,4-ndc) (Py)2S)(H2O)]n(ii) a Wherein n represents an infinite natural number, 1,4-ndc is 1, 4-naphthalenedicarboxylic acid, Py is2S is monosulfidine, the metal organic framework material belongs to a triclinic system, a space group is P-1, and unit cell parameters are as follows:
the preparation method of the metal organic framework material comprises the following steps of mixing Co (ClO) under sealed conditions, wherein the alpha is 69.163 degrees, the beta is 82.97 degrees, and the gamma is 64.352 degrees4)2·6H2Adding O, 1, 4-naphthalenedicarboxylic acid and monothiopyridine into deionized water, mixing, adding sodium hydroxide to regulate the pH value of the solution to 7-8, stirring, adding the solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at the constant temperature of 120-160 ℃ for 48-96h, and cooling to room temperature at the constant speed of 2-3 ℃/h, namely electrolyzing water to prepare the metal organic framework (Co (1,4-ndc) (Py) for hydrogen production reaction2S)(H2O)]nThe crystalline material, the chemical structural formula of the 1, 4-naphthalene diacid and the monothiopyridine are respectively as follows:
2. the method for preparing a metal-organic framework material for hydrogen production reaction by electrolyzing water according to claim 1, wherein the prepared metal-organic framework for hydrogen production reaction by electrolyzing water [ Co (1,4-ndc) (Py)2S)(H2O)]nAnd adding an excessive mixed solution of methanol and n-propanol with the volume ratio of 1:1 into the crystalline material and a mortar, grinding, performing ultrasonic treatment for 3-8 hours, and centrifuging to obtain the cobalt-based organic framework nanosheet.
3. The method for preparing the metal-organic framework material for hydrogen production reaction by electrolyzing water as claimed in claim 1, wherein the 1, 4-naphthalene diacid, monothiopyridine, Co (C)lO4)2·6H2The molar ratio of O is 1:1:2-2:1: 2.
4. The method for preparing a metal organic framework material for hydrogen production reaction by electrolyzing water as recited in claim 1, wherein the concentration of the sodium hydroxide is 0.05-0.2 mol/L.
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