CN107118217B - A kind of porphyrin copper complex and preparation method thereof for electro-catalysis oxygen evolution reaction - Google Patents
A kind of porphyrin copper complex and preparation method thereof for electro-catalysis oxygen evolution reaction Download PDFInfo
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- -1 porphyrin copper complex Chemical class 0.000 title claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001301 oxygen Substances 0.000 title claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 25
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KUYYVTYSTWLHPI-UHFFFAOYSA-N N1C2=CC([N]3)=CC=C3C=C(N3)C=CC3=CC([N]3)=CC=C3C=C1C(C#N)=C2C1=CC=CC=C1 Chemical compound N1C2=CC([N]3)=CC=C3C=C(N3)C=CC3=CC([N]3)=CC=C3C=C1C(C#N)=C2C1=CC=CC=C1 KUYYVTYSTWLHPI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000004323 axial length Effects 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910001431 copper ion Inorganic materials 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229910004039 HBF4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 150000004032 porphyrins Chemical class 0.000 abstract description 7
- 239000013110 organic ligand Substances 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 150000004699 copper complex Chemical class 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011365 complex material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- FUTVBRXUIKZACV-UHFFFAOYSA-L zinc;3-[18-(2-carboxyethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,23-diid-2-yl]propanoic acid Chemical compound [Zn+2].[N-]1C(C=C2C(=C(C=C)C(C=C3C(=C(C=C)C(=C4)[N-]3)C)=N2)C)=C(C)C(CCC(O)=O)=C1C=C1C(CCC(O)=O)=C(C)C4=N1 FUTVBRXUIKZACV-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- 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
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B01J35/33—
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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 porphyrin copper complex and preparation method thereof that the invention discloses a kind of for electro-catalysis oxygen evolution reaction, specifically disclose under a kind of lower temperature it is succinct, efficiently, green and based on 5,10, Metal-organic complex, preparation method and its application in electro-catalysis oxygen evolution reaction that 15,20- four cyano phenyl porphyrin organic ligands are constructed.Raw material selected by the present invention is 5,10,15,20- four cyano phenyl porphyrin organic ligands and Gerhardite, and obtained porphyrin copper coordination chemistry formula is [C108Cu2N20O4H0.25], monoclinic system, space group P2/a, cell parameter is axial length Shaft angle α=90.00 °, β=93.8488 (13) °, γ=90.00 °, unit cell volume arePorphyrin copper complex of the invention shows good catalytic performance in electro-catalysis oxygen evolution reaction, is 10mA/cm in current density2When overpotential for oxygen evolution be 1.66v (vs.RHE is relative to reversible hydrogen electrode).This method simple process only uses organic solvent, and recyclable three-waste free discharge.
Description
Technical field
The invention belongs to new material technology field, specifically disclose under a kind of lower temperature it is succinct, efficiently, green and base
The metal-organic framework materials (porphyrin copper complex) constructed in porphyrin organic ligand, preparation method and its urge analysis oxygen anti-in electricity
Application in answering.
Background technique
Hydrogen Energy is considered as 21st century most potential secondary energy sources.Alkaline water electrolytic hydrogen-preparing is Hydrogen Energy research and development
An important topic, the main reason for energy consumption is high, low efficiency in water electrolysis process first is that overpotential for oxygen evolution is higher.Anode mistake
Current potential is too high, and energy conversion efficiency can be lower, if one kind can be developed, preferably the electricity with lower overpotential for oxygen evolution is urged
Change analysis oxygen anodes material, then can push the preparation of hydrogen.
In in the past few decades, Metal-organic complex is as a kind of porous crystalline material that novel high is orderly, tool
The features such as having higher specific surface area, aperture controllable and can modifying, makes it become new in chemistry and materials science field and grinds
Study carefully one of hot spot.Compared with traditional molecular sieve and porous carbon materials, Metal-organic complex all shows latent in many fields
Application value, as greenhouse gases absorption with separate, it is the storage of energy gas, fluorescence probe, not right in the confinement of space
Claim catalysis, the transmitting of drug molecule and molecular magnetism etc..
It is research hotspot in recent years by the Metal-organic complex that porphyrin organic ligand and metal ion are constructed.
Since the modifiability of porphyrin ligand structure and variable coordination ability make metalloporphyrin complex have multifarious structure, thus
Show multifrequency nature and function, organic chemistry, material science, in terms of suffer from broad application prospect.
There are many document report synthetic methods and application of metalloporphyrin complex, such as Chinese patent CN102391269A to disclose in recent years
Using benzaldehyde and its derivative, pyrroles as raw material, it is prepared through multistep reactions such as condensation, coordination, substitutions containing heterocyclic substituted
The zinc protoporphyrin monomer molecule and its metal complex of group, and have studied it and preparing sensitized nano crystal TiO2In solar battery
Photoelectric properties；CN1962663A discloses a series of Tetrabenzothiazolyl porphyrin metal complexes, in the series complex
Heart metal is the bivalent metal ions such as barium, calcium, cadmium, cobalt, copper, mercury, magnesium, nickel, lead, palladium, platinum, barium, zinc；It is more reported in the literature its
Its metalloporphyrin complex (bibliography Farha, O.K., Shultz, A.M., Sarjeant, A.A., Nguyen, S.T., &Hupp,
J.T.J.Am.Chem.Soc.,2011,133(15),pp 5652–5655；Shu,J.,Qiu,Z.,Wei,Q.,Zhuang,J.,&
Tang,D.Sci Rep.2015；5:15113.；Shahroosvand,H.,Zakavi,S.,Sousaraei,A.,
Mohajerani, E. , &Mahmoudi, M.Dalton Trans., 2015,44,8364-8368), selection be mostly carboxylic acid or
The fragrant porphyrin of the functional group containing modification forms Metal-organic complex structure as ligand.These above-mentioned building complexs are made
Ligand is not directed to utilize four cyano phenyl porphyrin ligand 5,10,15,20- four cyano phenyl porphyrin (CNTCPP) and three water
It closes copper nitrate and constructs porphyrin copper complex, never reported application of the porphyrin copper complex in terms of oxygen is analysed in electro-catalysis.
Summary of the invention
The object of the present invention is to provide a kind of porphyrin copper complex, preparation method and its answering in electro-catalysis oxygen evolution reaction
With.
Raw material selected by the present invention is 5,10,15,20- four cyano phenyl porphyrin (CNTCPP) ligand and three nitric hydrates
Copper, obtained porphyrin copper complex show good catalytic performance in electro-catalysis oxygen evolution reaction, are 10mA/ in current density
cm2When overpotential for oxygen evolution be 1.66v (vs.RHE is relative to reversible hydrogen electrode).This method simple process only uses organic molten
Agent, and recyclable three-waste free discharge.
A kind of porphyrin copper complex of the present invention, molecular formula are [Cu (CNTCPP)], and wherein Cu is divalent ion,
CNTCPP is 5,10,15,20- four cyano phenyl porphyrin ligands, and chemical structural formula is as follows:
Complex structure belongs to monoclinic system P2/a space group, and the basic structural unit of crystal is passed through by asymmetric cell
(symmetry operation code is x, y, z to symmetry operation；0.5-x,y,-z；-x,-y,-z；05.+x ,-y, z) it obtains；In asymmetric cell by
Two CNTCPP ligands, two copper ion (Cu1, Cu2) compositions, copper ion Cu1 take four-coordination mode and four nitrogen-atoms phases
Connection, and this four nitrogen-atoms are respectively from the nitrogen-atoms (N1, N2, N3, N4) in a CNTCPP ligand；Copper ion Cu2
Four-coordination mode is taken to be connected with four nitrogen-atoms, this four nitrogen-atoms are that the nitrogen in a CNTCPP ligand is former respectively
Sub (N9, N10, N11, N12)；The distance between Cu1-Cu2 isThere is no join for four cyanogen roots in CNTCPP ligand
With coordination (attached drawing 1)；Its cell parameter is axial lengthShaft angle α
=90.00 °, β=93.8488 (13) °, γ=90.00 °, unit cell volume isZ=4.
The preparation method of porphyrin copper complex of the present invention, its step are as follows:
1,5,10,15,20- four cyano phenyl porphyrin (CNTCPP) ligands and Gerhardite are dissolved in N, N ' dimethyl
Formamide solution forms the mixed solution of homogeneous phase；The ratio of the mole dosage of ligand and metal copper ion is 1:5, is being mixed
In solution, the concentration of ligand is 0.005~0.007mmol/mL；
2, the pH value for adjusting above-mentioned mixed solution is 5~7, and the solution is then placed in polytetrafluoroethylene (PTFE) stainless steel cauldron
In, 800~1200 minutes are kept the temperature under the conditions of 60~100 DEG C, to obtain porphyrin copper complex of the present invention.
Wherein step (2) using acidic materials adjust mixed solution pH value, acidic materials be selected from it is following any one or
It is a variety of: HCl, H2SO4、HClO4、HBF4、NH2PO4、H3PO4；The reaction for adjusting pH value is in stirring, ultrasound or concussion state
Lower progress.
Porphyrin copper complex prepared by the present invention can be used for preparing catalysis material, photoelectromagnetic material, anti-biotic material, drug and carry
Body or nano-reactor.In particular, porphyrin copper complex prepared by the present invention has good urge in electro-catalysis oxygen evolution reaction
Change performance, is 10mA/cm in current density2When overpotential for oxygen evolution be 1.66v (vs.RHE is relative to reversible hydrogen electrode).
The present invention provides a kind of quick, easy, greens, efficient synthesis porphyrin copper complex method.With conventional method
It compares, the invention has the following outstanding advantages:
1, reaction solvent for use be easy to get, be inexpensive, green non-pollution；
2, reaction condition is simple, reaction can be carried out quickly, is energy saving, saving the time；
3, yield is high, ligand dosage is low, saves cost；
4, by the way that acidic materials are added, promote ligand hydrolysis, reduce ligand dosage, gained porphyrin copper complex yield is high；
5, complex shows good catalytic performance in electro-catalysis oxygen evolution reaction, is 10mA/cm in current density2When
Overpotential for oxygen evolution is 1.66v (vs.RHE is relative to reversible hydrogen electrode).This method extends porphyrin copper complex structure data, right
It studies porphyrin copper complex formation mechanism study, industrialization large-scale production and extends it in sides such as catalysis, nano-device preparations
The application in face has important directive significance.
To sum up, the present invention uses 5,10,15,20- four cyano phenyl porphyrin of porphyrin ligand under the conditions of solvent heat
(CNTCPP) ligand has synthesized novel porphyrin copper complex material with Gerhardite.This method is succinct, efficient, green, is
The data material for expanding porphyrin copper complex material provides effective guidance, to expansion porphyrin copper complex in catalysis, photoelectromagnetic
There are important values for the application in the fields such as material.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the structural schematic diagram of the dissymmetrical structure unit of complex prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD spectra of the porphyrin copper complex in the present invention；
Fig. 3: being the thermogravimetric curve of porphyrin copper complex；
Fig. 4: being the oxygen evolution reaction polarization curve of porphyrin copper complex；
Fig. 5: being the analysis oxygen column Fei Er curve spectrum of porphyrin copper complex；
Fig. 6: being the analysis oxygen ac impedance spectroscopy of porphyrin copper complex.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1: the present embodiment is related to the preparation of porphyrin copper complex:
(1) reactant 5,10,15,20- four cyano phenyl porphyrin (CNTCPP) and with Gerhardite press 1:5 molar ratio
It feeds intake.Accurately weigh 0.02g with assay balance, 5,10,15,20- four cyano phenyl porphyrin (CNTCPP) of 0.028mmol and
0.034g, 0.14mmol Gerhardite are in reaction vessel；Under room temperature, the anhydrous N of 5mL, N ' dimethylformamide is added
Stirring solvent 12 hours, stops reaction, reaction solution is filtered with filter paper, obtains blue-green filtrate；
(2) HBF is added to filtrate4Solution adjusts pH value to 6, and filtrate is then transferred to 25mL polytetrafluoroethyllining lining not
It becomes rusty in steel reaction kettle, is subsequently placed in 85 DEG C of constant temperature bellows and reacts 1000 minutes, obtain light blue crystal.
Elemental Analysis theory: C, 70.31；H,4.15；N, 15.18%；Perkin-Elmer model 240C
240 type elemental analyser test value of analyzerPE company: C, 70.02；H,4.65；N, 18.09%.The monocrystalline X- of complex is penetrated
Line diffraction, powder x-ray diffraction, thermogravimetric spectrogram difference are as shown in Figures 1 to 3.
Crystal structure is under the conditions of room temperature (293K), with Agilent Xcalibur Eos Gemini single crystal diffractometer
What instrument was collected.With graphite monochromator, λ (Cu K α) isIn a manner of the variable-speed scanning of ω -2 θ, multiscan is used
Program SADABS carries out absorption correction.Crystal structure is parsed using direct method with Sir97 program；With SHELXL-97 program
Structure refinement is carried out to F2 using complete matrix least square method.Anisotropy refine is carried out to all non-hydrogen atoms.Organic ligand
Hydrogen atom pass through geometrically symmetric generation (C-H).Complex crystal parameter is as shown in table 1, and structure is as shown in Figure 1.No
By two CNTCPP ligands, two copper ion (Cu1, Cu2) compositions in symmetrical cell；Copper ion Cu1 take four-coordination mode with
Four nitrogen-atoms are connected, and this four nitrogen-atoms be respectively from a CNTCPP ligand nitrogen-atoms (N1, N2, N3,
N4)；Copper ion Cu2 takes four-coordination mode to be connected with four nitrogen-atoms, this four nitrogen-atoms are from one respectively
Nitrogen-atoms (N9, N10, N11, N12) in CNTCPP ligand；The distance between Cu1-Cu2 isIn CNTCPP ligand
Four cyanogen roots do not participate in being coordinated；Its cell parameter is axial length
Shaft angle α=90.00 °, β=93.8488 (13) °, γ=90.00 °, unit cell volume areZ=4.
The powder x-ray diffraction of porphyrin copper complex manufactured in the present embodiment is as shown in Fig. 2, the curve 1 in Fig. 2 is logical
The cif file of crossing complex, which fits, to be come, and curve 2 is the measured curve of complex, by the actual measurement XRD spectra of complex and quasi-
The XRD spectra of conjunction compares, if the peak position and intensity of respective peaks can correspond to, that is, illustrates that corresponding crystal face has been grown
Whole, Atomic Arrangement is also consistent with crystal data, i.e., it is believed that complex has the structure being fitted in the cif file of the spectrogram.
The thermogravimetric spectrogram of porphyrin copper complex manufactured in the present embodiment at 90~280 DEG C as shown in figure 3, lose in system
The crystallization water and N, N ' solvent dimethylformamide, then complex can be stabilized to 550 DEG C, and complex decomposes after 550 DEG C.
Table 1: crystallographic parameter
Table 2: the typical bond distance's data of crystal (unit:)
Table 3: the typical bond angle data of crystal (unit: °)
Embodiment 2: the present embodiment is related to complex electro-catalysis oxygen evolution reaction:
For the analysis oxygen performance of research material, using three-electrode system in electrochemical workstation (Gamry Reference
600Instruments, USA) on tested.Porphyrin copper complex prepared by 5.0mg embodiment 1 as catalyst and
20.0 μ LNafion (5wt%) solution are dispersed in 1mL alcohol-water mixed solution (ethyl alcohol: the volume ratio of water is 1:1), ultrasound
Processing obtains uniform dispersion liquid in 1 hour.Then the 5.0 μ L dispersion liquids are supported on the glass-carbon electrode that diameter is 4 millimeters.Make
Use the KOH of 1.0M as electrolyte (with 30 minutes removing dissolved oxygens of pure oxygen gas bell), saturated calomel electrode as reference electrode,
High-purity platinum electrode is used as to electrode, and load has the glass-carbon electrode of catalyst as working electrode, with 5mV s-1Speed is swept to polarize
The measurement of curve.As shown in figure 4, measuring embodiment 1 in current density is 10mA/cm2When overpotential for oxygen evolution be 1.66v
(vs.RHE is relative to reversible hydrogen electrode), as shown in figure 5, curve 1, which represents experiment, tests obtained Tafel curve, curve 2
The slope for the Tafel curve that fitting obtains is represented, Tafel slope is 84.1mV/dec, as shown in fig. 6, porphyrin copper complex
Impedance in oxygen evolution reaction is up to 65 ohm.By above data as it can be seen that the porphyrin copper complex that the embodiment of the present invention 1 obtains
With good analysis oxygen catalytic activity.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (3)
1. a kind of application of porphyrin copper complex in electro-catalysis oxygen evolution reaction, the preparation method of the porphyrin copper complex,
Steps are as follows:
(1), 5,10,15,20- four cyano phenyl porphyrin ligands and Gerhardite are dissolved in N, N ' dimethylformamide is molten
Liquid forms the mixed solution of homogeneous phase；The ratio of the mole dosage of ligand and metal copper ion is 1:5, in mixed solution, is matched
The concentration of body is 0.005 ~ 0.007 mmol/mL；
(2), the pH value for adjusting the mixed solution is 5 ~ 7, is subsequently placed in polytetrafluoroethylene (PTFE) stainless steel cauldron, 60 ~ 100 DEG C
Under the conditions of keep the temperature 800 ~ 1200 minutes, obtain the porphyrin copper complex；
The porphyrin copper complex for electro-catalysis oxygen evolution reaction, molecular formula be Cu (CNTCPP), wherein Cu be divalent from
Son, 5,10,15,20- four cyano phenyl porphyrin ligand of CNTCPP；Complex structure belongs to monoclinic system P2/a space group, brilliant
The basic structural unit of body is to be obtained by asymmetric cell by symmetry operation, symmetry operation code be x, y, z, 0.5-x, y,
-z,-x, -y, -z,0.5+x, -y, z；By two ligand CNTCPP, two copper ion Cu1 and Cu2 groups in asymmetric cell
At the distance between Cu1 and Cu2 are 8.599；Four cyanogen roots in CNTCPP ligand do not participate in being coordinated；Cell parameter
For axial length a=15.3680 (2), b=17.1634 (2), c=33.5945 (6), shaft angle α=90.00 °, β=
93.8488 (13) °, γ=90.00 °, unit cell volume are V=8841.2 (2) 3, Z=4.
2. application of the porphyrin copper complex as described in claim 1 in electro-catalysis oxygen evolution reaction, it is characterised in that: step
It (2) is the pH value that mixed solution is adjusted using acidic materials, acidic materials are selected from HCl, H2SO4、HClO4、HBF4、NH2PO4、
H3PO4One of or it is a variety of.
3. application of the porphyrin copper complex as described in claim 1 in electro-catalysis oxygen evolution reaction, it is characterised in that: step
(2) reaction of pH value is adjusted described in be carried out under stirring, ultrasound or concussion state.
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Citations (2)
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|---|---|---|---|---|
| US6127356A (en) * | 1993-10-15 | 2000-10-03 | Duke University | Oxidant scavengers |
| CN103952145A (en) * | 2014-04-27 | 2014-07-30 | 中国石油大学(华东) | Ratio-type transition metal porphyran polymer luminescent oxygen sensing material |
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2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127356A (en) * | 1993-10-15 | 2000-10-03 | Duke University | Oxidant scavengers |
| CN103952145A (en) * | 2014-04-27 | 2014-07-30 | 中国石油大学(华东) | Ratio-type transition metal porphyran polymer luminescent oxygen sensing material |
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| Title |
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| EPR Spectra, Luminescence Data, and Radiationless Decay Processes of Copper(II) Porphyrins;Kurstan L. Cunningham，等;《Inorg. Chem.》;19971231;第36卷;第608-613页 * |
| Robotic sequential analysis of a library of metalloporphyrins as electrocatalysts for voltammetric nitric oxide sensors;Victoria Ryabova，等;《Analyst》;20050713;第130卷(第9期);第1245-1252页 * |
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