CN108187749A - A kind of preparation method of Multifunction electrolytic water sponge catalyst - Google Patents
A kind of preparation method of Multifunction electrolytic water sponge catalyst Download PDFInfo
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- CN108187749A CN108187749A CN201711472924.1A CN201711472924A CN108187749A CN 108187749 A CN108187749 A CN 108187749A CN 201711472924 A CN201711472924 A CN 201711472924A CN 108187749 A CN108187749 A CN 108187749A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 85
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 64
- 238000009987 spinning Methods 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000013110 organic ligand Substances 0.000 claims abstract description 13
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 102
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 235000012054 meals Nutrition 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000008247 solid mixture Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical class O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000003292 diminished effect Effects 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims 1
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 35
- 238000003860 storage Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003446 ligand Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000001338 self-assembly Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229920000767 polyaniline Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 239000002322 conducting polymer Substances 0.000 description 12
- 239000004020 conductor Substances 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000003421 catalytic decomposition reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/27—Cadmium
-
- 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 discloses a kind of preparation methods of Multifunction electrolytic water sponge catalyst, belong to electro-catalysis splitting water technical field, include the following steps：(1) preparation of cadmium base MOF：Using organic ligand and the interionic metal ligand coordination of cadmium metal, the supramolecular network structure being self-assembly of；(2) preparation of conductive polymer solution：It is blended to obtain conductive polymer solution using PANI DBSA, polyacrylonitrile and oiliness ATO solution；(3) it is molten to blow coating cadmium base MOF：By conductive polymer solution squeeze it is molten blow out spinning after be sufficiently mixed with nanometer cadmium base MOF powder；(4) preparation of sponge catalyst：Heating removes the excess of solvent for being filled in the first body of three-dimensional catalyst；In short, the advantages of sponge catalyst active current potential of the invention prepared is more, electric conductivity is excellent, high catalytic efficiency, good hydrogen storage effect.
Description
Technical field
The invention belongs to electro-catalysis splitting water technical fields, and in particular to a kind of Multifunction electrolytic water sponge catalyst
Preparation method.
Background technology
With being constantly progressive for economic fast development and science and technology, the energy and environment have extremely important in social development
Effect.In past 50 years, a large number of researchers are dedicated to studying, develop efficient, economic, the renewable sustainable energy.For
Realize that target of sustainable development, searching and exploitation green energy resource and high efficient energy sources equipment are extremely urgent.It is worth noting that, Hydrogen Energy
It is considered as the most clean, the efficient energy, obtaining Hydrogen Energy can be divided by the separation of natural air, the cracking of fossil energy
From or partial oxidation, photocatalysis Decomposition, biomass ferment conversion, electrolysis water；Wherein, electro-catalysis hydrolytic hydrogen production and oxygen processed cause
The extensive concern of global scientists, and electrolysis water is considered as one of method of production Hydrogen Energy of most prospect.
Electrolysis water is that liquid water is decomposed into oxygen (O by the electric power2) and hydrogen (H2) the phenomenon that.Due to the half of electrolysis water
Reaction (half-reaction of analysis oxygen) needs larger overpotential that could occur, and considerably increases the energy consumption of hydrogen manufacturing, therefore, exploitation is efficiently urged
The catalyst for changing oxygen evolution reaction is very necessary for the raising of hydrogen producing technology, while in hydrogen energy source, chlorine industry and solar energy
Use aspect is all very significant.
The efficient of hydrogen, safe storage and transport are also one of main bottleneck that hydrogen energy source utilizes.Existing hydrogen storage method is substantially
It is divided into 5 kinds, i.e. liquid hydrogen storage, high-pressure hydrogen storing, organic compound hydrogen storage, metallic compound hydrogen storage and adsorption hydrogen-storing, exists apparent
The defects of：Need there are one huge hydrogen infrastructure, it is of high cost, less economical the problems such as, from realizing commercial applications also
There is very big distance.And hydrogen such as prepares, conveys and fills at the mating basis on a large scale, and construction cost is big, the period is long.Existing system
Hydrogen technique and hydrogen storage technology be mostly maximum discharge, low-energy-efficiency process, Atom economy is poor, without sustainability, and with
The problems such as aggravation of the energy field to hydrogen demand, the sustainability in source and the efficient of storage and transportation, flexibility, shows day by day, becomes
Hydrogen Energy system is hindered to construct and perfect key factor.
Invention content
For the electrolysis water catalyst electric conductivity for preparing in the prior art is low, specific surface area is small, active current potential is few, cannot
Have both the function of hydrogen storage and because recycling rate of waterused is low caused by fatigue resistance difference the technical issues of, the present invention provides a kind of
The preparation method of Multifunction electrolytic water sponge catalyst.
The technical scheme is that：A kind of preparation method of Multifunction electrolytic water sponge catalyst, including following
Step：
(1) preparation of cadmium base MOF：By two water cadmium acetates, organic ligand, nitrogen source using mass ratio as 2:2:1 mixes and carries out
Grinding is uniform, obtains solid mixture；By tetrahydrofuran, ethyl alcohol, deionized water using volume ratio as 4:1:3 are uniformly mixed, and obtain
Mixed solvent；By the solid mixture and the mixed solvent with solid-to-liquid ratio with 1:2-4 is mixed, and is utilized and be ultrasonically treated 1-
1.5h obtains mixed solution；The mixed solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, with the heating of 10 DEG C/min
Rate is warming up to 140-150 DEG C, and isothermal reaction 15-20h, obtains reactant, and the reactant is cooled to room temperature, through centrifugation
Filtering, removes a layer crystalline solid, and the crystalline solid using the methanol of a concentration of 20%-80% is eluted 1-3 times, is finally done in vacuum
Cadmium base MOF is dried to obtain in dry case；It is acted on using organic ligand and the interionic metal-ligand coordinate of cadmium metal, self assembly shape
Into supramolecular network structure, 50-60 times and 200-300 times has been respectively increased compared to Ni-based MOF and chromium base MOF in electric conductivity,
Conducive to the catalytic decomposition of electrolysis water, improve production hydrogen rate, in addition, cadmium base MOF supramolecular network structures can also to the hydrogen of generation into
Row storage.
(2) preparation of conductive polymer solution：The PANI-DBSA of certain mass is taken to be dissolved in dimethyl sulfoxide solvent,
It is stirred at 75-80 DEG C to being completely dissolved, then adds polyacrylonitrile, after stirring 1-2h under room temperature, add ATO solution,
Be sufficiently stirred 10-12h, obtain blend solution, by the blend solution through being filtered under diminished pressure, vacuum defoamation, obtain conducting polymer
Solution, wherein, PANI-DBSA, dimethyl sulfoxide (DMSO), polyacrylonitrile, ATO solution mass ratio be 10:18:10:5；
(3) it is molten to blow coating cadmium base MOF：The cadmium base MOF is ground to nanometer grade powder, obtains a nanometer cadmium base MOF powder,
The nanometer cadmium base MOF powder and the conductive polymer solution are respectively added to advertise in pump and syringe pump, nanometer cadmium base
The mass ratio of MOF and conductive polymer solution is 3-5:1, by it is described advertise pump and syringe pump be connected to it is molten blow collection device, to
It is molten to blow in collection device while be blown into nanometer conductive polymer solution and nanometer cadmium base MOF powder, it obtains receiving after deposition modeling
Three-dimensional catalyst first body of the spinning and nanometer cadmium base MOF powder that rice conductive polymer solution is formed for matrix；By conducting polymer
Object Solution extrusion is molten blow out spinning after be sufficiently mixed with nanometer cadmium base MOF powder, compared to concentric package or mixing hair
Method of forming 3 D stereo and good dispersion are steeped, has the advantages that large specific surface area, active current potential exposure are more.
(4) preparation of sponge catalyst：Body at the beginning of the three-dimensional catalyst is cut into 1-3cm3Cubic block, then will
The cubic block is laid in pallet, is put into vacuum drying chamber, is warming up to 150-200 DEG C, heating rate is 2 DEG C/min, is protected
Warm 1-2h, heating remove the excess of solvent in the first body of three-dimensional catalyst, after being cooled to room temperature, obtain sponge catalyst.Heating
The excess of solvent for being filled in the first body of three-dimensional catalyst is removed, can further improve the porosity of sponge catalyst, and
And heating is conducive to be molded.
Further, the organic ligand for 1,2- diimidazoles ethane, Isosorbide-5-Nitrae-diimidazole butane, 1,3- diimidazoles propane,
Pyridine, 4-4 ' bipyridyls, N,N-dimethylformamide, terephthalic acid (TPA), thioacetamide 4,5- imidazole-2-carboxylic acids, 2- ethyls-
Any one in 4,5- imidazole-2-carboxylic acids.
Further, the nitrogen source is melamine, urea, ammonium sulfate, ammonium nitrate, solid amino acid, nitroaniline, idol
Any one in nitrogen bis-isobutyronitrile, aziridine.
Further, the ATO solution is into being grouped as by following weight percent：27.3-27.8% is nano oxidized
Tin, 2.2-2.7% nanometer antimony oxides, surplus are oil-based solvent.ATO solution is as a kind of conductive material, in dispersibility, resistance to work
Property, thermoplasticity, wearability have other conductive materials in safety, such as graphite, surfactant, metal powder are incomparable
Advantage.And the ATO solution of oiliness is easy to be merged with conducting polymer.
Further, the oil-based solvent is ethyl acetate, toluene, dimethylbenzene, ethyl alcohol, isopropanol, butanone, acetic acid fourth
Any one in ester.
Further, it is described it is molten blow coating cadmium base MOF technological parameter be：The delivery rate of the conductive polymer solution
For 30-40ml/h, the delivery rate of nanometer cadmium base MOF powder is 100-150g/h, and the back pressure of conductive polymer solution is
0.01-0.1MPa.Rational delivery rate can ensure conductive polymer solution spinning and nanometer cadmium base MOF powder reasonable
It uniformly mixes and is molded in proportioning.
Further, the molten collection device that blows includes collecting barrel mast, nozzle, stent, motor, rotary head, the stent packet
Include support baseboard, accommodate column one, accommodate column two and accommodate column three, it is described blessing column one, accommodate column two and accommodate column three successively from
Left-to-right is vertically fixed on the support baseboard, and the motor is clipped in the upper end for accommodating column one, the right end of rotary head and the electricity
The output shaft of machine is connected, and for the sprayer head clamp in the upper end for accommodating column two, the center of nozzle left end is equipped with meal outlet, it is described go out
Several micropore filament mouths for being surrounded by rounded distribution of powder mouth, the micropore filament mouth are connected with injection by forcing pipe
It pumping, is connected on the right side of the syringe pump and advertises pump, the pump of advertising is connected by running through the central tube of syringe pump with meal outlet,
For advertising pump described in fixed, described one end for collecting barrel mast is clamped the blessing column three with rotary head, the other end by bearing and
Sprinkler rotation connects.
Further, a port for collecting barrel mast, which is equipped with, is threadedly coupled mouth, and the threaded connection mouth is with passing through
Bearing is connected with the nozzle, and the another port for collecting barrel mast is equipped with through hole, and the left and right outside of the through hole is respectively equipped with L
Shape clamping joint, the L-shaped clamping joint are clamped with the rotary head, collect and the activity mat identical with surge drum column internal diameter is equipped in barrel mast
Piece, the removable insole pieces are close to through hole one end.
Further, it is described it is molten blow collection device method of work be：It assembles and molten blows collection device, then take said ratio
Nanometer cadmium base MOF powder and conductive polymer solution be respectively added to described advertise in pump and syringe pump；The motor is opened,
It drives the rotary head successively using motor and collects barrel mast and carry out positive and negative rotation, the positive and negative rotating speed of motor is 100-300r/
Min is divided into 3-5min between rotating, meanwhile, nanometer cadmium base MOF powder with the delivery rate of 100-150g/h by it is described go out powder
Mouthful, conductive polymer solution with the delivery rate of 30-40ml/h by micropore filament mouth, while to collect barrel mast in jet spinning
And powder, it is made to be sufficiently mixed in the case where collecting barrel mast positive and negative rotation, deposition forms three-dimensional catalyst just body；Collection barrel mast is removed,
Pass through the through hole that removable insole pieces is pushed integrally to release body at the beginning of three-dimensional catalyst using shaft.It is driven and collected using motor
Barrel mast carries out rotating with specific rate and time interval, and the spinning superposition presentation that can promote conductive polymer solution is random
Property, increase that its three-dimensional is three-dimensional, and the active for collecting barrel mast is also beneficial to improve the dispersibility of nanometer cadmium base MOF powder, i.e.,
It is uniformly mixed with the spinning of conductive polymer solution.
Compared with prior art, beneficial effects of the present invention are：
(1) present invention is acted on using organic ligand and the interionic metal-ligand coordinate of cadmium metal, and what is be self-assembly of is super
Molecular network structure, 50-60 times and 200-300 times has been respectively increased compared to Ni-based MOF and chromium base MOF in electric conductivity, conducive to electricity
The catalytic decomposition of Xie Shui improves production hydrogen rate, in addition, cadmium base MOF supramolecular network structures can also store the hydrogen of generation.
(2) present invention is blended to obtain conducting polymer molten using PANI-DBSA, polyacrylonitrile and oiliness ATO solution
Conductive polymer solution is squeezed to form a nanometer spinning by liquid by micropore, wherein PANI-DBSA, it is polyacrylonitrile blended after have
Good electric conductivity, and the elasticity modulus of spinning can be increased, improve recycling rate of waterused.ATO solution as a kind of conductive material,
There are other conductive materials in dispersibility, resistance to activity, thermoplasticity, wearability, safety, such as graphite, surfactant, metal
The incomparable advantage such as powder.And oiliness ATO solution is easy to be merged with conducting polymer.
(3) present invention by conductive polymer solution squeeze it is molten blow out after spinning carried out with nanometer cadmium base MOF powder it is fully mixed
It closes, compared to concentric package or mixed foaming method of forming 3 D stereo and good dispersion, there is large specific surface area, activity electricity
The advantages of position exposure is more.
(4) the molten collection device that blows of the invention drives collection barrel mast to be carried out with specific rate and time interval using motor
Rotating can promote the spinning of conductive polymer solution to be superimposed and no regularity is presented, and it is three-dimensional to increase its three-dimensional, and surge drum
The active of column is also beneficial to improve the dispersibility of nanometer cadmium base MOF powder, i.e., is uniformly mixed with the spinning of conductive polymer solution.
In addition, the interior bottom for collecting barrel mast is equipped with removable insole pieces, bottom is equipped with through hole, after body at the beginning of three-dimensional catalyst is deposited and to be formed,
It passes through through hole that removable insole pieces is pushed integrally to release body at the beginning of three-dimensional catalyst using shaft, takes out more convenient.
In short, being had by sponge catalyst prepared by the present invention, large specific surface area, active current potential is more, electric conductivity is excellent
Good, high catalytic efficiency, hydrogen storage effect be good and the advantages that high recycling rate.
Description of the drawings
Fig. 1 is the molten overall structure diagram for blowing collection device of the present invention；
Fig. 2 is the dimensional structure diagram of the nozzle of the present invention；
Fig. 3 is the sectional view of the collection barrel mast of the present invention.
Wherein, 1- collects barrel mast, 11- is threadedly coupled mouth, 12- through holes, 13-L shapes clamping joint, 14- removable insole pieces, 2- spray
Head, 21- meal outlets, 22- micropores filament mouth, 3- stents, 31- support baseboards, 32- accommodate column one, 33- accommodates column two, 34- accommodates
Column three, 4- motors, 5- rotary heads, 6- forcing pipes, 7- syringe pumps, 8- advertise pump, 9- central tubes.
Specific embodiment
Below in conjunction with the accompanying drawings 1-3 come to the present invention be further described in detail：
Embodiment 1
A kind of preparation method of Multifunction electrolytic water sponge catalyst, includes the following steps：
(1) preparation of cadmium base MOF：By two water cadmium acetates, organic ligand 1,2- diimidazoles ethane, nitrogen source melamine with matter
Amount is than being 2:2:1 mixes and is ground uniformly, obtains solid mixture；By tetrahydrofuran, ethyl alcohol, deionized water with volume ratio
It is 4:1:3 are uniformly mixed, and obtain mixed solvent；By solid mixture and mixed solvent with solid-to-liquid ratio with 1:2 mixing, and utilize super
Sonication 1h, obtains mixed solution；Mixed solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, with the heating of 10 DEG C/min
Rate is warming up to 140 DEG C, and isothermal reaction 15h, obtains reactant, reactant is cooled to room temperature, and through centrifugal filtration, removes layer
Crystalline solid using a concentration of 20% methanol is eluted 1 time, cadmium base MOF is finally dried to obtain in vacuum drying chamber by crystalline solid；
Using organic ligand 1,2- diimidazoles ethane is acted on the interionic metal-ligand coordinate of cadmium metal, the oversubscription being self-assembly of
Sub-network structure, 50 times and 200 times have been respectively increased compared to Ni-based MOF and chromium base MOF in electric conductivity, conducive to the catalysis of electrolysis water
It decomposes, production hydrogen rate is improved, in addition, cadmium base MOF supramolecular network structures can also store the hydrogen of generation.
(2) preparation of conductive polymer solution：The PANI-DBSA of certain mass is taken to be dissolved in dimethyl sulfoxide solvent,
It is stirred at 75 DEG C to being completely dissolved, then adds polyacrylonitrile, after stirring 1-2h under room temperature, add ATO solution acetic acid
Ethyl ester is sufficiently stirred 10h, obtains blend solution, by blend solution through being filtered under diminished pressure, vacuum defoamation, it is molten to obtain conducting polymer
Liquid, wherein, PANI-DBSA, dimethyl sulfoxide (DMSO), polyacrylonitrile, ATO solution mass ratio be 10:18:10:5；Wherein, ATO is molten
Liquid ethyl acetate is into being grouped as by following weight percent：27.3% nano tin dioxide, 2.2% nanometer antimony oxide, surplus
For oil-based solvent.ATO solution ethyl acetate is as a kind of conductive material, in dispersibility, resistance to activity, thermoplasticity, wearability, safety
There are other conductive materials, such as the advantage that graphite, surfactant, metal powder are incomparable in property.And the ATO of oiliness is molten
Liquid is easy to be merged with conducting polymer.
(3) it is molten to blow coating cadmium base MOF：Cadmium base MOF is ground to nanometer grade powder, a nanometer cadmium base MOF powder is obtained, will receive
Rice cadmium base MOF powder and conductive polymer solution are respectively added to advertise in pump and syringe pump, nanometer cadmium base MOF and conducting polymer
The mass ratio of object solution is 3:1, will advertise pump and syringe pump be connected to it is molten blow collection device, blow in collection device while blow to molten
Enter nanometer conductive polymer solution and nanometer cadmium base MOF powder, obtain being formed with nanometer conductive polymer solution after deposition modeling
Spinning and nanometer cadmium base MOF powder for matrix three-dimensional catalyst just body；By conductive polymer solution squeeze it is molten blow out spinning
Be sufficiently mixed afterwards with nanometer cadmium base MOF powder, compared to concentric package or mixed foaming method of forming 3 D stereo and
Good dispersion has the advantages that large specific surface area, active current potential exposure are more.It is molten blow coating cadmium base MOF technological parameter be：It is conductive
The delivery rate of polymer solution is 30ml/h, and the delivery rate of nanometer cadmium base MOF powder is 100g/h, conductive polymer solution
Back pressure be 0.01MPa.Rational delivery rate can ensure the spinning of conductive polymer solution and nanometer cadmium base MOF powder
End uniformly mixes and is molded in rational proportion.
Wherein, the molten collection device that blows includes collecting barrel mast 1, nozzle 2, stent 3, motor 4, rotary head 5, and stent 3 includes support
Bottom plate 31, accommodate column 1, accommodate column 2 33 and accommodate column 3 34, accommodate column 1, accommodate column 2 33 and accommodate column 3 34 according to
Secondary to be vertically fixed on from left to right on support baseboard 31, motor 4 is clipped in the upper end for accommodating column 1, right end and the motor 4 of rotary head 5
Output shaft be connected, nozzle 2 is clipped in the upper end for accommodating column 2 33, and the center of 2 left end of nozzle is equipped with meal outlet 21, meal outlet
The 21 several micropore filament mouths 22 for being surrounded by rounded distribution, micropore filament mouth 22 are connected with syringe pump by forcing pipe 6
7, the right side of syringe pump 7, which is connected with, advertises pump 8, advertises pump 8 and is connected by running through the central tube 9 of syringe pump 7 with meal outlet 21, is added
Hold column 3 34 for fixation advertise pump 8, one end of collection barrel mast 1 is clamped with rotary head 5, and the other end is rotated by bearing and nozzle 2
Connection.The a port for collecting barrel mast 1 is equipped with threaded connection mouth 11, is threadedly coupled mouth 11 and is connected with by bearing with nozzle 2, receives
The another port for collecting barrel mast 1 is equipped with through hole 12, and the left and right outside of through hole 12 is respectively equipped with L-shaped clamping joint 13, L-shaped clamping joint
13 are clamped with rotary head 5, collect and the removable insole pieces 14 identical with collecting 1 internal diameter of barrel mast are equipped in barrel mast 1, and removable insole pieces 14 are close to pass through
It perforates 12 one end.
Wherein, it is molten blow collection device method of work be：Assemble the molten nanometer cadmium base for blowing collection device, then taking said ratio
MOF powder and conductive polymer solution are respectively added to advertise in pump 8 and syringe pump 7；Motor 4 is opened, utilizes motor 4 successively band
Turn head 5 and collection barrel mast 1 carry out positive and negative rotation, and the positive and negative rotating speed of motor 4 is 100r/min, and 3min is divided between rotating,
Meanwhile nanometer cadmium base MOF powder with the delivery rate of 100g/h by meal outlet 21, conductive polymer solution is with the confession of 30ml/h
To rate by micropore filament mouth 22, while to jet spinning and powder in barrel mast 1 is collected, it is made to collect 1 rotating of barrel mast
It is sufficiently mixed under dynamic, deposition forms three-dimensional catalyst just body；It removes and collects barrel mast 1, pushed using shaft across through hole 12
Removable insole pieces 14 integrally release body at the beginning of three-dimensional catalyst.It is driven using motor and collects barrel mast 1 with specific rate and between the time
Every carrying out rotating, the spinning of conductive polymer solution can be promoted to be superimposed, no regularity is presented, it is three-dimensional to increase its three-dimensional, and
The active for collecting barrel mast 1 is also beneficial to improve the dispersibility of nanometer cadmium base MOF powder, i.e., is mixed with the spinning of conductive polymer solution
It closes uniform.
(4) preparation of sponge catalyst：Body at the beginning of three-dimensional catalyst is cut into 1cm3Cubic block, then by cubic block
It is laid in pallet, is put into vacuum drying chamber, be warming up to 150 DEG C, heating rate is 2 DEG C/min, keeps the temperature 1h, and heating removes three
The excess of solvent in the first body of catalyst is tieed up, after being cooled to room temperature, obtains sponge catalyst.Heating removes and is filled in three-dimensional catalytic
The excess of solvent of the first body of agent, can further improve the porosity of sponge catalyst, and heats and be conducive to be molded.
The current efficiency of sponge catalyst manufactured in the present embodiment is 78%, and electrochemical hydrogen storage capacity is 932mAh/g.
Embodiment 2
A kind of preparation method of Multifunction electrolytic water sponge catalyst, includes the following steps：
(1) preparation of cadmium base MOF：By two water cadmium acetates, organic ligand 1,3- diimidazoles propane, nitrogen source aziridine with matter
Amount is than being 2:2:1 mixes and is ground uniformly, obtains solid mixture；By tetrahydrofuran, ethyl alcohol, deionized water with volume ratio
It is 4:1:3 are uniformly mixed, and obtain mixed solvent；By solid mixture and mixed solvent with solid-to-liquid ratio with 1:3 mixing, and utilize super
Sonication 1.3h, obtains mixed solution；Mixed solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, with the liter of 10 DEG C/min
Warm rate is warming up to 145 DEG C, and isothermal reaction 17h, obtains reactant, reactant is cooled to room temperature, and through centrifugal filtration, removes
Crystalline solid using a concentration of 50% methanol is eluted 2 times, cadmium base is finally dried to obtain in vacuum drying chamber by layer crystalline solid
MOF；Using organic ligand 1,3- diimidazoles propane is acted on the interionic metal-ligand coordinate of cadmium metal, is self-assembly of
Supramolecular network structure, 55 times and 250 times have been respectively increased compared to Ni-based MOF and chromium base MOF in electric conductivity, conducive to electrolysis water
Catalytic decomposition improves production hydrogen rate, in addition, cadmium base MOF supramolecular network structures can also store the hydrogen of generation.
(2) preparation of conductive polymer solution：The PANI-DBSA of certain mass is taken to be dissolved in dimethyl sulfoxide solvent,
It is stirred at 78 DEG C to being completely dissolved, then adds polyacrylonitrile, after stirring 1.5h under room temperature, add ATO solution ethanols,
Be sufficiently stirred 11h, obtain blend solution, by blend solution through being filtered under diminished pressure, vacuum defoamation, obtain conductive polymer solution,
In, PANI-DBSA, dimethyl sulfoxide (DMSO), polyacrylonitrile, ATO solution ethanols mass ratio be 10:18:10:5；Wherein, ATO solution
Ethyl alcohol is into being grouped as by following weight percent：27.5% nano tin dioxide, 2.5% nanometer antimony oxide, surplus are oiliness
Solvent.ATO solution has other to lead as a kind of conductive material in dispersibility, resistance to activity, thermoplasticity, wearability, safety
Electric material, such as the advantage that graphite, surfactant, metal powder are incomparable.And the ATO solution of oiliness is easy to gather with conduction
Object is closed to be merged.
(3) it is molten to blow coating cadmium base MOF：Cadmium base MOF is ground to nanometer grade powder, a nanometer cadmium base MOF powder is obtained, will receive
Rice cadmium base MOF powder and conductive polymer solution are respectively added to advertise in pump and syringe pump, nanometer cadmium base MOF and conducting polymer
The mass ratio of object solution is 4:1, will advertise pump and syringe pump be connected to it is molten blow collection device, blow in collection device while blow to molten
Enter nanometer conductive polymer solution and nanometer cadmium base MOF powder, obtain being formed with nanometer conductive polymer solution after deposition modeling
Spinning and nanometer cadmium base MOF powder for matrix three-dimensional catalyst just body；By conductive polymer solution squeeze it is molten blow out spinning
Be sufficiently mixed afterwards with nanometer cadmium base MOF powder, compared to concentric package or mixed foaming method of forming 3 D stereo and
Good dispersion has the advantages that large specific surface area, active current potential exposure are more.It is molten blow coating cadmium base MOF technological parameter be：It is conductive
The delivery rate of polymer solution is 30-40ml/h, and the delivery rate of nanometer cadmium base MOF powder is 125g/h, conducting polymer
The back pressure of solution is 0.05MPa.Rational delivery rate can ensure the spinning of conductive polymer solution and nanometer cadmium base
MOF powder is uniformly mixed and is molded in rational proportion.
Wherein, the molten collection device that blows includes collecting barrel mast 1, nozzle 2, stent 3, motor 4, rotary head 5, and stent 3 includes support
Bottom plate 31, accommodate column 1, accommodate column 2 33 and accommodate column 3 34, accommodate column 1, accommodate column 2 33 and accommodate column 3 34 according to
Secondary to be vertically fixed on from left to right on support baseboard 31, motor 4 is clipped in the upper end for accommodating column 1, right end and the motor 4 of rotary head 5
Output shaft be connected, nozzle 2 is clipped in the upper end for accommodating column 2 33, and the center of 2 left end of nozzle is equipped with meal outlet 21, meal outlet
The 21 several micropore filament mouths 22 for being surrounded by rounded distribution, micropore filament mouth 22 are connected with syringe pump by forcing pipe 6
7, the right side of syringe pump 7, which is connected with, advertises pump 8, advertises pump 8 and is connected by running through the central tube 9 of syringe pump 7 with meal outlet 21, is added
Hold column 3 34 for fixation advertise pump 8, one end of collection barrel mast 1 is clamped with rotary head 5, and the other end is rotated by bearing and nozzle 2
Connection.The a port for collecting barrel mast 1 is equipped with threaded connection mouth 11, is threadedly coupled mouth 11 and is connected with by bearing with nozzle 2, receives
The another port for collecting barrel mast 1 is equipped with through hole 12, and the left and right outside of through hole 12 is respectively equipped with L-shaped clamping joint 13, L-shaped clamping joint
13 are clamped with rotary head 5, collect and the removable insole pieces 14 identical with collecting 1 internal diameter of barrel mast are equipped in barrel mast 1, and removable insole pieces 14 are close to pass through
It perforates 12 one end.
Wherein, it is molten blow collection device method of work be：Assemble the molten nanometer cadmium base for blowing collection device, then taking said ratio
MOF powder and conductive polymer solution are respectively added to advertise in pump 8 and syringe pump 7；Motor 4 is opened, utilizes motor 4 successively band
Turn head 5 and collection barrel mast 1 carry out positive and negative rotation, and the positive and negative rotating speed of motor 4 is 200r/min, and 4min is divided between rotating,
Meanwhile nanometer cadmium base MOF powder with the delivery rate of 125g/h by meal outlet 21, conductive polymer solution is with the confession of 35ml/h
To rate by micropore filament mouth 22, while to jet spinning and powder in barrel mast 1 is collected, it is made to collect 1 rotating of barrel mast
It is sufficiently mixed under dynamic, deposition forms three-dimensional catalyst just body；It removes and collects barrel mast 1, pushed using shaft across through hole 12
Removable insole pieces 14 integrally release body at the beginning of three-dimensional catalyst.It is driven using motor and collects barrel mast 1 with specific rate and between the time
Every carrying out rotating, the spinning of conductive polymer solution can be promoted to be superimposed, no regularity is presented, it is three-dimensional to increase its three-dimensional, and
The active for collecting barrel mast 1 is also beneficial to improve the dispersibility of nanometer cadmium base MOF powder, i.e., is mixed with the spinning of conductive polymer solution
It closes uniform.
(4) preparation of sponge catalyst：Body at the beginning of three-dimensional catalyst is cut into 2cm3Cubic block, then by cubic block
It is laid in pallet, is put into vacuum drying chamber, be warming up to 175 DEG C, heating rate is 2 DEG C/min, keeps the temperature 1.5h, and heating removes
Excess of solvent in the first body of three-dimensional catalyst, after being cooled to room temperature, obtains sponge catalyst.Heating removing is filled in three-dimensional and urges
The excess of solvent of the first body of agent, can further improve the porosity of sponge catalyst, and heats and be conducive to be molded.
The current efficiency of sponge catalyst manufactured in the present embodiment is 85%, and electrochemical hydrogen storage capacity is 954mAh/g.
Embodiment 3
A kind of preparation method of Multifunction electrolytic water sponge catalyst, includes the following steps：
(1) preparation of cadmium base MOF：By two water cadmium acetates, organic ligand 4-4 ' bipyridyls, nitrogen source urea using mass ratio as 2:
2:1 mixes and is ground uniformly, obtains solid mixture；By tetrahydrofuran, ethyl alcohol, deionized water using volume ratio as 4:1:3
It is uniformly mixed, obtains mixed solvent；By solid mixture and mixed solvent with solid-to-liquid ratio with 1:4 mixing, and utilize supersound process
1.5h obtains mixed solution；Mixed solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, with the heating rate of 10 DEG C/min
150 DEG C, and isothermal reaction 20h are warming up to, reactant is obtained, reactant is cooled to room temperature, through centrifugal filtration, removes layer crystallization
Crystalline solid using a concentration of 80% methanol is eluted 3 times, cadmium base MOF is finally dried to obtain in vacuum drying chamber by body；It utilizes
Organic ligand 4-4 ' bipyridyls are acted on the interionic metal-ligand coordinate of cadmium metal, the Supramolecular Network knot being self-assembly of
Structure, electric conductivity have been respectively increased 60 times and 300 times compared to Ni-based MOF and chromium base MOF, conducive to the catalytic decomposition of electrolysis water, have carried
High yield hydrogen rate, in addition, cadmium base MOF supramolecular network structures can also store the hydrogen of generation.
(2) preparation of conductive polymer solution：The PANI-DBSA of certain mass is taken to be dissolved in dimethyl sulfoxide solvent,
It is stirred at 80 DEG C to being completely dissolved, then adds polyacrylonitrile, after stirring 2h under room temperature, add ATO solution acetic acid fourths
Ester is sufficiently stirred 12h, obtains blend solution, by blend solution through being filtered under diminished pressure, vacuum defoamation, obtain conductive polymer solution,
Wherein, PANI-DBSA, dimethyl sulfoxide (DMSO), polyacrylonitrile, ATO solution butyl acetates mass ratio be 10:18:10:5；Wherein,
ATO solution butyl acetates are into being grouped as by following weight percent：27.8% nano tin dioxide, 2.7% nanometer antimony oxide,
Surplus is oil-based solvent.ATO solution is as a kind of conductive material, in dispersibility, resistance to activity, thermoplasticity, wearability, safety
There are other conductive materials, such as the advantage that graphite, surfactant, metal powder are incomparable.And the ATO solution of oiliness is easy
It is merged in conducting polymer.
(3) it is molten to blow coating cadmium base MOF：Cadmium base MOF is ground to nanometer grade powder, a nanometer cadmium base MOF powder is obtained, will receive
Rice cadmium base MOF powder and conductive polymer solution are respectively added to advertise in pump and syringe pump, nanometer cadmium base MOF and conducting polymer
The mass ratio of object solution is 5:1, will advertise pump and syringe pump be connected to it is molten blow collection device, blow in collection device while blow to molten
Enter nanometer conductive polymer solution and nanometer cadmium base MOF powder, obtain being formed with nanometer conductive polymer solution after deposition modeling
Spinning and nanometer cadmium base MOF powder for matrix three-dimensional catalyst just body；By conductive polymer solution squeeze it is molten blow out spinning
Be sufficiently mixed afterwards with nanometer cadmium base MOF powder, compared to concentric package or mixed foaming method of forming 3 D stereo and
Good dispersion has the advantages that large specific surface area, active current potential exposure are more.It is molten blow coating cadmium base MOF technological parameter be：It is conductive
The delivery rate of polymer solution is 40ml/h, and the delivery rate of nanometer cadmium base MOF powder is 150g/h, conductive polymer solution
Back pressure be 0.1MPa.Rational delivery rate can ensure the spinning of conductive polymer solution and nanometer cadmium base MOF powder
End uniformly mixes and is molded in rational proportion.
Wherein, the molten collection device that blows includes collecting barrel mast 1, nozzle 2, stent 3, motor 4, rotary head 5, and stent 3 includes support
Bottom plate 31, accommodate column 1, accommodate column 2 33 and accommodate column 3 34, accommodate column 1, accommodate column 2 33 and accommodate column 3 34 according to
Secondary to be vertically fixed on from left to right on support baseboard 31, motor 4 is clipped in the upper end for accommodating column 1, right end and the motor 4 of rotary head 5
Output shaft be connected, nozzle 2 is clipped in the upper end for accommodating column 2 33, and the center of 2 left end of nozzle is equipped with meal outlet 21, meal outlet
The 21 several micropore filament mouths 22 for being surrounded by rounded distribution, micropore filament mouth 22 are connected with syringe pump by forcing pipe 6
7, the right side of syringe pump 7, which is connected with, advertises pump 8, advertises pump 8 and is connected by running through the central tube 9 of syringe pump 7 with meal outlet 21, is added
Hold column 3 34 for fixation advertise pump 8, one end of collection barrel mast 1 is clamped with rotary head 5, and the other end is rotated by bearing and nozzle 2
Connection.The a port for collecting barrel mast 1 is equipped with threaded connection mouth 11, is threadedly coupled mouth 11 and is connected with by bearing with nozzle 2, receives
The another port for collecting barrel mast 1 is equipped with through hole 12, and the left and right outside of through hole 12 is respectively equipped with L-shaped clamping joint 13, L-shaped clamping joint
13 are clamped with rotary head 5, collect and the removable insole pieces 14 identical with collecting 1 internal diameter of barrel mast are equipped in barrel mast 1, and removable insole pieces 14 are close to pass through
It perforates 12 one end.
Wherein, it is molten blow collection device method of work be：Assemble the molten nanometer cadmium base for blowing collection device, then taking said ratio
MOF powder and conductive polymer solution are respectively added to advertise in pump 8 and syringe pump 7；Motor 4 is opened, utilizes motor 4 successively band
Turn head 5 and collection barrel mast 1 carry out positive and negative rotation, and the positive and negative rotating speed of motor 4 is 300r/min, and 5min is divided between rotating,
Meanwhile nanometer cadmium base MOF powder with the delivery rate of 150g/h by meal outlet 21, conductive polymer solution is with the confession of 40ml/h
To rate by micropore filament mouth 22, while to jet spinning and powder in barrel mast 1 is collected, it is made to collect 1 rotating of barrel mast
It is sufficiently mixed under dynamic, deposition forms three-dimensional catalyst just body；It removes and collects barrel mast 1, pushed using shaft across through hole 12
Removable insole pieces 14 integrally release body at the beginning of three-dimensional catalyst.It is driven using motor and collects barrel mast 1 with specific rate and between the time
Every carrying out rotating, the spinning of conductive polymer solution can be promoted to be superimposed, no regularity is presented, it is three-dimensional to increase its three-dimensional, and
The active for collecting barrel mast 1 is also beneficial to improve the dispersibility of nanometer cadmium base MOF powder, i.e., is mixed with the spinning of conductive polymer solution
It closes uniform.
(4) preparation of sponge catalyst：Body at the beginning of three-dimensional catalyst is cut into 3cm3Cubic block, then by cubic block
It is laid in pallet, is put into vacuum drying chamber, be warming up to 200 DEG C, heating rate is 2 DEG C/min, keeps the temperature 2h, and heating removes three
The excess of solvent in the first body of catalyst is tieed up, after being cooled to room temperature, obtains sponge catalyst.Heating removes and is filled in three-dimensional catalytic
The excess of solvent of the first body of agent, can further improve the porosity of sponge catalyst, and heats and be conducive to be molded.
The current efficiency of sponge catalyst manufactured in the present embodiment is 81%, and electrochemical hydrogen storage capacity is 938mAh/g.
Using above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the content on specification, it is necessary to determine its technical scope according to right.
Claims (9)
1. a kind of preparation method of Multifunction electrolytic water sponge catalyst, which is characterized in that include the following steps：
(1) preparation of cadmium base MOF：By two water cadmium acetates, organic ligand, nitrogen source using mass ratio as 2:2:1 mixes and is ground
Uniformly, solid mixture is obtained；By tetrahydrofuran, ethyl alcohol, deionized water using volume ratio as 4:1:3 are uniformly mixed, and are mixed
Solvent；By the solid mixture and the mixed solvent with solid-to-liquid ratio with 1:2-4 is mixed, and is utilized and be ultrasonically treated 1-1.5h,
Obtain mixed solution；The mixed solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, with the heating rate of 10 DEG C/min
140-150 DEG C, and isothermal reaction 15-20h are warming up to, obtains reactant, the reactant is cooled to room temperature, through centrifuging
Filter, removes a layer crystalline solid, and the crystalline solid using the methanol of a concentration of 20%-80% is eluted 1-3 times, is finally being dried in vacuo
Cadmium base MOF is dried to obtain in case；
(2) preparation of conductive polymer solution：The PANI-DBSA of certain mass is taken to be dissolved in dimethyl sulfoxide solvent, in 75-
It is stirred at 80 DEG C to being completely dissolved, then adds polyacrylonitrile, after stirring 1-2h under room temperature, add ATO solution, fully stir
Mix 10-12h, obtain blend solution, by the blend solution through being filtered under diminished pressure, vacuum defoamation, obtain conductive polymer solution,
In, PANI-DBSA, dimethyl sulfoxide (DMSO), polyacrylonitrile, ATO solution mass ratio be 10:18:10:5；
(3) it is molten to blow coating cadmium base MOF：The cadmium base MOF is ground to nanometer grade powder, a nanometer cadmium base MOF powder is obtained, by institute
State nanometer cadmium base MOF powder and the conductive polymer solution be respectively added to advertise in pump and syringe pump, nanometer cadmium base MOF with
The mass ratio of conductive polymer solution is 3-5:1, by it is described advertise pump and syringe pump be connected to it is molten blow collection device, blow receipts to molten
Nanometer conductive polymer solution and nanometer cadmium base MOF powder are blown into simultaneously in acquisition means, is obtained after deposition modeling with conductive nano
Three-dimensional catalyst first body of the spinning and nanometer cadmium base MOF powder that polymer solution is formed for matrix；
(4) preparation of sponge catalyst：Body at the beginning of the three-dimensional catalyst is cut into 1-3cm3Cubic block, then will described in
Cubic block is laid in pallet, is put into vacuum drying chamber, is warming up to 150-200 DEG C, heating rate is 2 DEG C/min, keeps the temperature 1-
2h, heating remove the excess of solvent in the first body of three-dimensional catalyst, after being cooled to room temperature, obtain sponge catalyst.
A kind of 2. preparation method of Multifunction electrolytic water sponge catalyst as described in claim 1, which is characterized in that institute
Organic ligand is stated as 1,2- diimidazoles ethane, 1,4- diimidazoles butane, 1,3- diimidazoles propane, pyridine, 4-4 ' bipyridyls, N, N-
Any one in dimethylformamide, terephthalic acid (TPA), 4,5- imidazole-2-carboxylic acids, 2- ethyl -4,5- imidazole-2-carboxylic acids.
A kind of 3. preparation method of Multifunction electrolytic water sponge catalyst as described in claim 1, which is characterized in that institute
Nitrogen source is stated as melamine, urea, ammonium sulfate, ammonium nitrate, solid amino acid, nitroaniline, azodiisobutyronitrile, aziridine
In any one.
A kind of 4. preparation method of Multifunction electrolytic water sponge catalyst as described in claim 1, which is characterized in that institute
That states ATO solution is dissolved as oil-based solvent.
A kind of 5. preparation method of Multifunction electrolytic water sponge catalyst as described in claim 1, which is characterized in that institute
It is into being grouped as by following weight percent to state ATO solution：27.3-27.8% nano tin dioxides, 2.2-2.7% are nano oxidized
Antimony, surplus are oil-based solvent.
A kind of 6. preparation method of Multifunction electrolytic water sponge catalyst as claimed in claim 4, which is characterized in that institute
Oil-based solvent is stated as any one in ethyl acetate, toluene, dimethylbenzene, ethyl alcohol, isopropanol, butanone, butyl acetate.
A kind of 7. preparation method of Multifunction electrolytic water sponge catalyst as described in claim 1, which is characterized in that institute
Stating the molten technological parameter for blowing coating cadmium base MOF is：The delivery rate of the conductive polymer solution be 30-40ml/h, nanometer cadmium
The delivery rate of base MOF powder is 100-150g/h, and the back pressure of conductive polymer solution is 0.01-0.1MPa.
A kind of 8. preparation method of Multifunction electrolytic water sponge catalyst as described in claim 1, which is characterized in that institute
It states the molten collection device that blows to include collecting barrel mast (1), nozzle (2), stent (3), motor (4), rotary head (5), the stent (3) includes
Support baseboard (31) accommodates column one (32), accommodates column two (33) and accommodates column three (34), and the blessing column one (32) accommodates column
Two (33) and blessing column three (34) are vertically fixed on from left to right successively on the support baseboard (31), and the motor (4) is clipped in
The upper end of column one (32) is accommodated, the right end of rotary head (5) is connected with the output shaft of the motor (4), and the nozzle (2) is clipped in blessing
The upper end of column two (33), the center of nozzle (2) left end are equipped with meal outlet (21), and being surrounded by for meal outlet (21) is in
Several micropore filament mouths (22) of circular distribution, the micropore filament mouth (22) are connected with syringe pump (7) by forcing pipe (6),
It is connected on the right side of the syringe pump (7) and advertises pump (8), the pump (8) of advertising is by running through the central tubes (9) of syringe pump (7)
It is connected with meal outlet (21), it is described to accommodate column three (34) for advertising pump (8), described one end for collecting barrel mast (1) described in fixation
It is clamped with rotary head (5), the other end is rotatablely connected by bearing and nozzle (2).
A kind of 9. preparation method of Multifunction electrolytic water sponge catalyst as claimed in claim 8, which is characterized in that institute
State collect barrel mast (1) a port be equipped be threadedly coupled mouth (11), it is described threaded connection mouth (11) with by bearing with it is described
Nozzle (2) is connected, and the another port for collecting barrel mast (1) is equipped with through hole (12), and the left and right outside of the through hole (12) is respectively
Equipped with L-shaped clamping joint (13), the L-shaped clamping joint (13) is clamped with the rotary head (5), collects in barrel mast (1) and is equipped with and collection
The identical removable insole pieces (14) of barrel mast (1) internal diameter, the removable insole pieces (14) are close to through hole (12) one end.
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| CN108187749B (en) | 2020-06-23 |
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