CN108997587A - It is a kind of for water electrolysis hydrogen production reaction metal-organic framework material and its nanometer sheet material preparation method - Google Patents
It is a kind of for water electrolysis hydrogen production reaction metal-organic framework material and its nanometer sheet material preparation method Download PDFInfo
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- CN108997587A CN108997587A CN201810645684.9A CN201810645684A CN108997587A CN 108997587 A CN108997587 A CN 108997587A CN 201810645684 A CN201810645684 A CN 201810645684A CN 108997587 A CN108997587 A CN 108997587A
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- organic framework
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- hydrogen production
- water electrolysis
- electrolysis hydrogen
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 71
- 229910001868 water Inorganic materials 0.000 title claims abstract description 64
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 239000013384 organic framework Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 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 claims description 2
- 238000002050 diffraction method Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract 1
- 229910001453 nickel ion Inorganic materials 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 description 30
- 150000003624 transition metals Chemical class 0.000 description 29
- 235000013495 cobalt Nutrition 0.000 description 17
- 239000013078 crystal Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 7
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical class SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 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
- 238000009738 saturating Methods 0.000 description 2
- 239000000725 suspension Substances 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- AIUIJBDEQKTMHT-UHFFFAOYSA-N perchloric acid;hydrate Chemical compound O.OCl(=O)(=O)=O AIUIJBDEQKTMHT-UHFFFAOYSA-N 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
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000003313 weakening effect Effects 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
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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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
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Abstract
The present invention relates to a kind of preparation methods of the nanometer chip architecture of metal-organic framework material and its material for water electrolysis hydrogen production reaction.Belong to the technical field of crystalline material.The structural formula of the material are as follows: [Co (1,4-ndc) (Py2S)(H2O)]n.Wherein, n is indicated just infinite, and Isosorbide-5-Nitrae-ndc indicates Isosorbide-5-Nitrae-naphthalene diacid, Py2S indicates single thiopyridines.The two-dimensional network structure that the metal-organic framework material is made up of transition metal ions and organic ligand 1,4- naphthalene diacid and assistant ligand list thiopyridines coordinate bond or intermolecular force.Cobalt, the nickel ion of the preferred divalent of transition metal ions.The metal-organic framework material has good thermal stability.Metal organic frame from the above mentioned is the nanometer sheet of the preparation of presoma because it has relatively excellent proton transport and electron exchange ability and highly exposed active site, it is made to have preferable water electrolysis hydrogen production performance.Also it is expected as a kind of efficient Novel electrolytic water producing hydrogen, catalyzing agent material.
Description
Technical field
The present invention designs a kind of metal-organic framework material and its nanometer piece preparation method for water electrolysis hydrogen production reaction,
Belong to metal-organic framework material and nanometer sheet technical field.
Background technique
Water electrolysis hydrogen production technology is the following effective way for obtaining green energy resource hydrogen energy source.And platinum is as efficient electrolysis water
Catalyst for preparing hydrogen, at high price, earth reserves are less, are easy to happen catalyst poisoning phenomenon, are unfavorable for hydrogen energy source and hydrogen passes through
The harmonious development of Ji, therefore efficient base metal elctro-catalyst is explored, the regeneration and efficient and rational utilize for hydrogen energy source have
There is profound significance.
MOF is by organic ligand and the highly crystallized solid-state material formed with metallic atom node by coordinate bond, tool
The features such as standby structure is adjustable, vdiverse in function, and active site is abundant, large specific surface area, and cellular structure height is regular.However, already
The MOFs material of report still has proton transport and electron exchange rate slower caused by the dimensional effect of micron level, catalysis
The defects of active site exposure is insufficient, the difference of electric conductivity, and the preparation strategy energy by the way that MOFs to be ultrasonically formed to ultrathin nanometer piece
Effectively solve the weakening in bring performance due to these defects.Wherein, two-dimentional transition metal cobalt-based organic framework materials and
Its nanometer sheet because of its low dimensional structures, highly exposed active site in water electrolysis hydrogen production catalyst using upper, present compared with
For superior performance, it is expected to become a kind of efficient Novel electrolytic water producing hydrogen, catalyzing agent material.
Summary of the invention
The present invention provides one kind and is based on 1 for many defects caused by the dimensional effect of current MOFs material micron rank,
The preparation method of 4- naphthalene diacid and single thiopyridines transition metal cobalt-based organic framework materials constructed and its nanometer sheet and its in electricity
Solve the application on water catalyst for preparing hydrogen.It include an independent Co of crystallography in the metal framework structure basic unit2+Ion,
One 1,4-ndc ligand and a Py2S assistant ligand.One Co2+By being four oxygen atoms on two Isosorbide-5-Nitrae-ndc ligands,
One Py2Nitrogen-atoms on S connects to form two-dimentional monokaryon organic frame.The compound not only has good water electrolysis hydrogen production
Catalytic performance, and the more standby Hydrogen Evolution Performance for being better than presoma of nanometer sheet obtained by it for precursor preparation.
A kind of metal-organic framework material and its nanometer piece preparation method for water electrolysis hydrogen production reaction, chemical general formula
For [Co (1,4-ndc) (Py2S)(H2O)]n；Wherein, n indicates that just infinite natural number, Isosorbide-5-Nitrae-ndc indicate Isosorbide-5-Nitrae-naphthalene diacid,
Py2S indicates single thiopyridines.Organic ligand 1,4-ndc and assistant ligand Py2The chemical molecular formula of S is respectively C12H8O4And
C10H8N2S, molecular structural formula are respectively as follows:
The crystalline material belongs to anorthic system, space group P-1, cell parameter are as follows: α=69.163 °, β=82.97 °, γ=64.352 °.
The preparation method of the transition metal cobalt-based organic framework materials, steps are as follows, and steps are as follows, in air-proof condition
Under, by Co (Cl4)2·6H2O, Isosorbide-5-Nitrae-naphthalene diacid, single thiopyridines are add to deionized water mixing, then hydrogen-oxygen are added thereto
Changing sodium to adjust pH value of solution is 7-8, is added in the stainless steel cauldron equipped with polytetrafluoroethyllining lining after stirring, at 120-160 DEG C
After lower isothermal reaction 48-96h, room temperature, the i.e. metal organic frame [Co of water electrolysis hydrogen production reaction are cooled at the uniform velocity with 2-3 DEG C/h
(1,4-ndc)(Py2S)(H2O)]nCrystalline material.
Wherein organic ligand 1,4- naphthalene diacid, assistant ligand list thiopyridines, cobaltous perchlorate molar ratio be 1:1:2-2:1:
2, organic ligand Isosorbide-5-Nitrae-naphthalene diacid of every 0.1 mmol corresponds to the deionized water of 4mL, and the concentration of the sodium hydroxide is 0.05-
0.2mol/L。
Transition metal cobalt-based organic framework materials and nanometer sheet are the preparation method comprises the following steps: take the cobalt-based organic frame of certain mass
The crystal of material, with addition volume ratio in mortar to be ground 30 minutes after the methanol of 1:1 and the mixed solution of isopropanol, ultrasonic 3-
It handles within 8 hours, the nanometer sheet being centrifuged.By the preparation of cobalt-based organic frame nano material nanometer sheet with a thickness of 1.52 ±
0.32nm, specific surface area 2.6264m2/g。
Described transition metal organic framework materials [Co (the 1,4-ndc) (Py2S)(H2O)]nAnd its corresponding nanometer sheet exists
Water electrolysis hydrogen production catalyst field is provided with application prospect.
Wherein room temperature according to the present invention refers both to the environment temperature under normal pressure.
The present invention relates to the Opacity in lens method of metal organic frame, test method and data research.
The present invention relates to metal organic frame electro-chemical tests to analyze data research.
The present invention relates to the test of metal organic frame X-ray single crystal diffractometer and data researches.
The present invention develops one kind and is based on Isosorbide-5-Nitrae-naphthalene diacid and single thiopyridines transition cobalt-based metal organic frame crystalline material,
It is demonstrated experimentally that the material and its for precursor preparation nanometer sheet for the catalysis characteristics of water electrolysis hydrogen production, can be applied to be electrolysed
Water catalyst for preparing hydrogen Material Field.
It the present invention further discloses the growing method of such metal organic frame crystal, is obtained by hydro-thermal method culture
's.Structure determination is carried out to crystal using the small molecule type Advances in crystal X-ray diffraction instrument of Japanese Rigaku company, utilizes graphite list
Color device, wavelength X=0.071073nm Mo K alpha ray measure the data such as diffracted intensity and cell parameter under 120K, and with scanning
Technology carries out empirical absorption correction to collected data, and acquired results use Shelxtl-97 program to parse with direct method, use
Complete matrix least square method amendment.It is as follows to obtain crystallographic data.
This experiment has the advantage that due to taking above technical scheme
(1) synthetic method is simple, favorable reproducibility, yield height and, the temperature of easily controllable reaction system lower to temperature requirement
Degree；
(2) the auxiliary with containing sulphur atom of the crystalline material is synthesized, and sulphur atom has electro-catalysis HER performance and is greatly facilitated
Effect.Therefore the MOFs material constructed using fluorine-containing organic ligand, the electric conductivity and electro-catalysis HER of superior material can be shown
Performance；
(3) crystalline material is two-dimensional layer, and two-dimentional MOFs material surface has largely exposed metallic site, these
The presence of unsaturated sites is very important for improving catalytic performance.
(4) metal organic frame from the above mentioned is that the nanometer sheet of the preparation of presoma is passed because it has superior proton
Defeated and electron exchange ability and highly exposed active site, make it have preferable water electrolysis hydrogen production performance.Such as figure
Shown in 7-8, the performance of nanometer sheet is much better than bulk material.
Detailed description of the invention
Fig. 1 is transition metal organic framework materials [Co (1,4-ndc) (Py2S)(H2O)]nCoordination context diagram.
Fig. 2 is transition metal organic framework materials [Co (1,4-ndc) (Py2S)(H2O)]nFor the nanometer sheet of precursor preparation
Net structure char.
Fig. 3 is prepared transition metal organic framework materials [Co (1,4-ndc) (Py2S)(H2O)]nAnd its nanometer sheet
Powder diagram.Wherein, the corresponding curve of number 1 is the X-ray diffractogram of simulation, the corresponding transition gold for test of number 2
Belong to organic framework materials [Co (1,4-ndc) (Py2S)(H2O)]nX-ray diffractogram.Corresponding number 3 is test by transition gold
Belong to organic framework materials [Co (1,4-ndc) (Py2S)(H2O)]nFor the X-ray diffractogram of the nanometer sheet of precursor preparation.
Fig. 4 is transition metal organic framework materials [Co (1,4-ndc) (Py prepared by embodiment 12S)(H2O)]nSweep
Tracing.
Fig. 5 is transition metal organic framework materials [Co (1,4-ndc) (Py prepared by embodiment 12S)(H2O)]nIt is saturating
Penetrate figure.
Fig. 6 is prepared by transition metal organic framework materials [Co (1,4-ndc) (Py2S)(H2O)]nNanometer sheet it is saturating
Penetrate figure.
Fig. 7 is transition metal organic framework materials [Co (1,4-ndc) (Py prepared by embodiment 12S)(H2O)]nAnd its
The linear scan cyclic voltammetry curve figure of nanometer sheet.The corresponding curve of number 1 is transition metal organic framework materials [Co (1,4-
ndc)(Py2S)(H2O)]nLinear scan cyclic voltammetry curve figure.Number 2 is corresponding to have machine frame by transition metal for test
Frame material [Co (1,4-ndc) (Py2S)(H2O)]nFor the linear scan cyclic voltammetry curve figure of the nanometer sheet of precursor preparation.
Fig. 8 is transition metal organic framework materials [Co (1,4-ndc) (Py prepared by embodiment 12S)(H2O)]nAnd its
The Tafel curve figure of nanometer sheet.The corresponding curve of number 1 is transition metal organic framework materials [Co (1,4-ndc) (Py2S)
(H2O)]nTafel curve figure.Corresponding number 2 is test by transition metal organic framework materials [Co (1,4-ndc)
(Py2S)(H2O)]nFor the Tafel curve figure of the nanometer sheet of precursor preparation.
Fig. 9 is transition metal organic framework materials [Co (1,4-ndc) (Py prepared by embodiment 12S)(H2O)]nAnd its
The AC impedance figure of nanometer sheet.The corresponding curve of number 1 is transition metal organic framework materials [Co (1,4-ndc) (Py2S)
(H2O)]nAC impedance figure.Corresponding number 2 is test by transition metal organic framework materials [Co (1,4-ndc)
(Py2S)(H2O)]nFor the AC impedance figure of the nanometer sheet of precursor preparation.
Figure 10 is embodiment 7 by transition metal organic framework materials [Co (1,4-ndc) (Py2S)(H2O)]nFor forerunner's system
Standby nanometer sheet is 10mA cm in current density-2Under be up to 36 hours stability test curves.
Specific embodiment
Following embodiments be it is illustrative, be not restrictive, guarantor of the invention cannot be limited with following embodiments
Protect range.The raw material of the invention is commercially available.
Raw materials used in embodiment can obtain from market.Six perchloric acid hydrate cobalts analyze pure, Alpha；1,4- naphthalene two
Acid analyzes pure, Jinan perseverance；Single thiopyridines analyze pure, Jinan perseverance；NaOH analyzes pure, Jinan perseverance；
Embodiment 1
Under air-proof condition, by 0.2mmol Co (Cl4)2·6H2O (20mg), 0.1mmol Isosorbide-5-Nitrae-naphthalene diacid (20mg),
The mono- thiopyridines of 0.1mmol (18mg), which are added in the deionized water of 4mL, to be mixed, then sodium hydrate regulator solution is added thereto
PH is 7, is added in the stainless steel cauldron equipped with polytetrafluoroethyllining lining after stirring, the isothermal reaction 72h at 140 DEG C, with 2-3
DEG C/h is at the uniform velocity cooled to room temperature, obtain purple bulk crystals, i.e. transition metal cobalt-based organic framework materials [Co (Isosorbide-5-Nitrae-ndc)
(Py2S)(H2O)]nCrystalline material, structure are shown in the related content of attached drawing 1-9.
Embodiment 2
Under air-proof condition, by 0.1mmol Co (Cl4)2·6H2O (10mg), 0.1mmol1,4- naphthalene diacid (20mg),
The mono- thiopyridines of 0.1mmol (18mg), are added in the deionized water of 4mL and mix, then sodium hydrate regulator solution is added thereto
PH is 7, is added in the stainless steel cauldron equipped with polytetrafluoroethyllining lining after stirring, the isothermal reaction 96h at 140 DEG C, with
2-3 DEG C/h is at the uniform velocity cooled to room temperature, obtains purple bulk crystals, i.e. transition metal cobalt-based organic framework materials [Co (Isosorbide-5-Nitrae-
ndc)(Py2S)(H2O)]nCrystalline material.
Embodiment 3
Under air-proof condition, by 0.2mmol Co (Cl4)2·6H2O (20mg), 0.1mmol1,4- naphthalene diacid (20mg),
The mono- thiopyridines of 0.1mmol (18mg), are added in the deionized water of 4mL and mix, then sodium hydrate regulator solution is added thereto
PH is 8, is added in the stainless steel cauldron equipped with polytetrafluoroethyllining lining after stirring, the isothermal reaction 96h at 120 DEG C, with
2-3 DEG C/h is at the uniform velocity cooled to room temperature, obtains purple bulk crystals, i.e. transition metal cobalt-based organic framework materials [Co (Isosorbide-5-Nitrae-
ndc)(Py2S)(H2O)]nCrystalline material.
Embodiment 4
Under air-proof condition, by 0.1mmol Co (Cl4)2·6H2O (10mg), 0.1mmol1,4- naphthalene diacid (20mg),
The mono- thiopyridines of 0.1mmol (18mg), are added in the deionized water of 4mL and mix, then sodium hydrate regulator solution is added thereto
PH is 7, is added in the stainless steel cauldron equipped with polytetrafluoroethyllining lining after stirring, the isothermal reaction 72h at 120 DEG C, with
2-3 DEG C/h is at the uniform velocity cooled to room temperature, obtains purple bulk crystals, i.e. transition metal cobalt-based organic framework materials [Co (Isosorbide-5-Nitrae-
ndc)(Py2S)(H2O)]nCrystalline material.
Embodiment 5
Under air-proof condition, by 0.2mmol Co (Cl4)2·6H2O (20mg), 0.1mmol1,4- naphthalene diacid (20mg),
The mono- thiopyridines of 0.1mmol (18mg), are added in the deionized water of 4mL and mix, then sodium hydrate regulator solution is added thereto
PH is 7, is added in the stainless steel cauldron equipped with polytetrafluoroethyllining lining after stirring, the isothermal reaction 60h at 160 DEG C, with
2-3 DEG C/h is at the uniform velocity cooled to room temperature, obtains purple bulk crystals, i.e. transition metal cobalt-based organic framework materials [Co (Isosorbide-5-Nitrae-
ndc)(Py2S)(H2O)]nCrystalline material.
Embodiment 6
Under air-proof condition, by 0.2mmol Co (Cl4)2·6H2O (20mg), 0.1mmol1,4- naphthalene diacid (20mg),
The mono- thiopyridines of 0.1mmol (18mg), are added in the deionized water of 4mL and mix, then sodium hydrate regulator solution is added thereto
PH is 8, is added in the stainless steel cauldron equipped with polytetrafluoroethyllining lining after stirring, the isothermal reaction 72h at 140 DEG C, with
2-3 DEG C/h is at the uniform velocity cooled to room temperature, obtains purple bulk crystals, i.e. transition metal cobalt-based organic framework materials [Co (Isosorbide-5-Nitrae-
ndc)(Py2S)(H2O)]nCrystalline material.
Embodiment 7
Take transition metal cobalt-based organic framework materials [Co (the 1,4-ndc) (Py arbitrarily obtained in above-described embodiment 1-62S)
(H2O)]nTransition metal cobalt-based organic framework materials [Co (1,4-ndc) (Py of crystalline material2S)(H2O)]nCrystalline material 0.2g,
It is scattered in the methanol of 5 mL, the mixed solution of the normal propyl alcohol of 5mL is ground 30 minutes in mortar, is stood 10 minutes, is taken upper layer clear
Liquid centrifugation obtains transition metals cobalt base organic framework materials [Co (1,4-ndc) (Py2S)(H2O)]nCrystalline material is corresponding to be received
Rice piece, the results are shown in attached figure 3,7-10.
Embodiment 8
MOFs 10mg obtained is taken, the deionized water that the Nafion and 1.8mL of 0.2mL is added carries out ultrasound 30min, makes
Be completely dispersed after obtain suspension, the above-mentioned suspension of 5 μ L is then pipetted with liquid-transfering gun, glass-carbon electrode is added dropwise to, in room temperature
Under be dried, in 0.5M H2SO4Under tested.
The above embodiments are only the preferred technical solution of the present invention, and are not construed as limitation of the invention, this Shen
Please in embodiment and embodiment in feature in the absence of conflict, can mutual any combination.Protection model of the invention
The technical solution that should be recorded with claim is enclosed, the equivalent replacement side of technical characteristic in the technical solution recorded including claim
Case is protection scope.Equivalent replacement i.e. within this range is improved, also within protection scope of the present invention.
Claims (9)
1. a kind of metal-organic framework material for water electrolysis hydrogen production reaction, which is characterized in that the metal-organic framework material
Chemical molecular formula be [Co (1,4-ndc) (Py2S)(H2O)]n；Wherein, n indicates that just infinite natural number, Isosorbide-5-Nitrae-ndc are Isosorbide-5-Nitrae-
Naphthalene diacid, Py2S is single thiopyridines, includes an independent Co of crystallography in the metal framework structure basic unit2+Ion,
One 1,4- naphthalene diacid ligand and a Py2S assistant ligand, a Co2+By being four oxygen on two 1,4- naphthalene diacid ligands
Atom, a Py2Nitrogen-atoms on S connects the two-dimentional monokaryon organic framework materials for the layer structure to be formed.
2. the metal-organic framework material according to claim 1 for water electrolysis hydrogen production reaction, which is characterized in that described
1,4- naphthalene diacid and the chemical structural formulas of single thiopyridines be respectively as follows:
3. the metal-organic framework material according to claim 1 for water electrolysis hydrogen production reaction, which is characterized in that the crystalline substance
State material belongs to anorthic system, space group P-1, cell parameter are as follows:α=
69.163 °, β=82.97 °, γ=64.352 °.
4. the preparation side of the metal-organic framework material according to claim 1-3 for water electrolysis hydrogen production reaction
Method, which is characterized in that steps are as follows, under air-proof condition, by Co (Cl4)2·6H2O, Isosorbide-5-Nitrae-naphthalene diacid, single thiopyridines are added
It is mixed into deionized water, then it is 7-8 that sodium hydrate regulator solution pH is added thereto, is added after stirring and polytetrafluoroethylene (PTFE) is housed
In the stainless steel cauldron of liner, at 120-160 DEG C after isothermal reaction 48-96h, room temperature is cooled at the uniform velocity with 2-3 DEG C/h, i.e.,
Metal organic frame [Co (1,4-ndc) (Py of water electrolysis hydrogen production reaction2S)(H2O)]nCrystalline material.
5. the preparation method of the metal-organic framework material according to claim 4 for water electrolysis hydrogen production reaction, special
Sign is, takes metal organic frame [Co (Isosorbide-5-Nitrae-ndc) (Py of the water electrolysis hydrogen production being prepared reaction2S)(H2O)]nCrystalline state material
Material, it is 3-8 hours ultrasonic after excessive volume ratio is added in mortar to grind after the methanol of 1:1 and the mixed solution of normal propyl alcohol
Processing, centrifugation obtain cobalt-based organic frame nanometer sheet.
6. the preparation method of the metal-organic framework material according to claim 4 for water electrolysis hydrogen production reaction, special
Sign is, the organic ligand Isosorbide-5-Nitrae-naphthalene diacid, assistant ligand list thiopyridines, cobaltous perchlorate molar ratio be 1:1:2-2:1:
2。
7. the preparation method of the metal-organic framework material according to claim 4 for water electrolysis hydrogen production reaction, special
Sign is that the concentration of the sodium hydroxide is 0.05-0.2mol/L.
8. the metal-organic framework material according to claim 1-3 for water electrolysis hydrogen production reaction is in electrolysis water
As the application of catalyst in hydrogen production process.
9. application according to claim 8, which includes being used for electrolysis water using claim 1-3 is described in any item
The cobalt-based organic frame nanometer sheet material that the metal-organic framework material of hydrogen production reaction is prepared.
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| CN112191273A (en) * | 2020-10-12 | 2021-01-08 | 中国科学技术大学 | High-entropy coordination polymer catalyst for oxygen production by electrolyzing water and preparation method and application thereof |
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| CN113788957A (en) * | 2021-10-22 | 2021-12-14 | 福州大学 | Preparation of sulfur-containing metal organic coordination polymer material and application thereof in photocatalytic hydrogen production |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343257A (en) * | 2019-07-16 | 2019-10-18 | 三峡大学 | A kind of more chloro cobalt-based composite materials, preparation method and applications |
| CN110343257B (en) * | 2019-07-16 | 2021-11-09 | 三峡大学 | Polychlorinated cobalt-based composite material, preparation method and application thereof |
| CN112191273A (en) * | 2020-10-12 | 2021-01-08 | 中国科学技术大学 | High-entropy coordination polymer catalyst for oxygen production by electrolyzing water and preparation method and application thereof |
| CN112934262A (en) * | 2021-02-01 | 2021-06-11 | 北京理工大学 | Nickel-substituted tungsten-oxygen cluster organic framework material and preparation method and application thereof |
| CN112934262B (en) * | 2021-02-01 | 2021-10-26 | 北京理工大学 | Nickel-substituted tungsten-oxygen cluster organic framework material and preparation method and application thereof |
| CN113788957A (en) * | 2021-10-22 | 2021-12-14 | 福州大学 | Preparation of sulfur-containing metal organic coordination polymer material and application thereof in photocatalytic hydrogen production |
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