CN113501849B - Mononuclear cobalt complex, and preparation method and application thereof - Google Patents
Mononuclear cobalt complex, and preparation method and application thereof Download PDFInfo
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- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 abstract description 18
- 239000001301 oxygen Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 4
- -1 radical acetate Chemical class 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000295146 Gallionellaceae Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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Abstract
The invention discloses a mononuclear cobalt complex with a chemical general formula of Co (bipyalk) and (OAc)2Wherein bipyalk is 2,2'- ([2,2' -bipyridine ]]-6,6' -dimethyl) bis (propan-2-ol), OAc being the radical acetate. The invention also discloses a preparation method and application of the mononuclear cobalt complex. The mononuclear cobalt complex can be used for preparing oxygen by catalytic oxidation of water under the electrocatalysis condition.
Description
Technical Field
The invention relates to a mononuclear cobalt complex, a preparation method and application thereof, and belongs to the field of electrocatalysts.
Background
In the context of artificial photosynthesis, oxygen evolution reactions (OER, 2H)2O→O2+4H++4e-) A particularly challenging reaction is the kinetic bottleneck for the direct storage of solar energy in chemical fuels by water splitting processes. Since it is difficult to achieve multi-step electron/proton transfer by forming O — O bonds, the reaction kinetics is slow; therefore, active and stable catalysts are needed to reduce this barrier to promote the highly active rapid oxidation water reaction in aqueous media.
At present, the research of the water oxidizing agent by utilizing the complex of the noble metals ruthenium and iridium has certain results, so that the search for the first row of analogues which are cheap and rich in earth as substitutes is very attractive. In order to form the high oxidation state metal of the catalytically active site, the metal complex catalysts generally need to be operated at relatively high overpotentials. This means that the catalytic oxidation of water by such metal complexes requires harsh conditions, and the ligand must be designed to stabilize the high oxidation state of the metal center and strongly resist the degradation of the ligand.
Therefore, the current metal complex mainly selects noble metals to reduce the requirements on the performance of the ligand, but the cost is undoubtedly increased; or the first row transition metal is selected, but the typical ligand selection of the metal cannot stably exist in the catalytic water oxidation process due to the lack of sufficient electron donor power or the incapability of adapting to the oxidation condition, is easy to degrade, or can only play a catalytic role in an alkaline environment, and cannot meet the practical requirement.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention firstly discloses a mononuclear cobalt complex, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a mononuclear cobalt complex characterized by: the chemical formula is Co (bipyalk) and (OAc)2Wherein bipyalk is 2,2'- ([2,2' -bipyridine ]]-6,6' -dimethyl) bis (propan-2-ol), OAc being the radical acetate.
The present application utilizes 2,2'- ([2,2' -bipyridine)]-6,6' -dimethyl) bis (propan-2-ol) fixed centre cobalt atom, alkoxy group of pyridylalkoxy compound allowing proton coupled electron transfer and its strong sigma-And pi-The donor power is beneficial for the metal to obtain a very high oxidation state. The benzyl group of the aromatic pyridine ring is protected by the methyl group, and stronger combination and degradation resistance are provided in the catalytic turnover process. In addition, the ligand has two additional benefits: its broad solubility in aqueous and non-aqueous solvents, and the anisotropic ligand field enhances the geometrically relevant redox properties of its complexes.
At present, most of the first row transition metal complexes are used as water oxidants and are mainly carried out under alkaline conditions or only carried out in organic solvents, wherein part of the first row transition metal complexes have poor solubility in water and organic systems and can only be plated on the surfaces of FTO or ITO. The mononuclear cobalt complex can be dissolved in water and an organic solvent, can be used for preparing oxygen by electrocatalytic oxidation of water under neutral and acidic conditions, has no degradation phenomenon after electrocatalysis, and has high catalytic efficiency and overpotential lower than that of the existing cobalt complex.
By utilizing the mononuclear cobalt complex, the oxidation of water is expanded to an acidic environment, the application range of the metal complex catalyst is expanded to the acidic environment, the selectable range of an oxygen evolution environment is increased, and the oxygen evolution environment is more flexible.
The mononuclear cobalt complexes of the present application have the following structural formula (i):
secondly, the application also discloses a preparation method of the mononuclear cobalt complex, which comprises the following steps: dissolving cobalt acetate tetrahydrate and bipyalk in ethanol, stirring and reacting for 6-7 hours at the temperature of 50-60 ℃ in a light-proof environment, taking out and carrying out rotary evaporation, adding n-hexane, and crystallizing at the temperature of-30 to-50 ℃ in the light-proof environment to obtain the mononuclear cobalt complex.
Bipyalk in this application refers to 2,2' - ([2,2' -bipyridine ] -6,6' -dimethyl) bis (propan-2-ol).
In order to improve the reaction efficiency and ensure the quality of the obtained product, the molar ratio of the cobalt acetate tetrahydrate to the bipyalk is 1.0-1.4: 1, the excessive cobalt acetate tetrahydrate is beneficial to complete reaction of bipyalk, the ligand loss is reduced, and the production cost is reduced.
The molar ratio of ethanol to bipyalk was 500-700: 1, the excessive ethanol can ensure the sufficient dissolution of bipyalk on one hand, and on the other hand, the large polarity of the ethanol is utilized, which is beneficial to improving the reaction efficiency and is beneficial to the next step of separating out single crystals.
The molar ratio of n-hexane to bipyalk is 40-60: 1, the mixture of n-hexane with small polarity and ethanol with large polarity is beneficial to separating out single crystals, and meanwhile, the concentration is also close to the saturated concentration as much as possible, so that the difficulty of growing the single crystals is reduced, and the production efficiency is improved.
The application also discloses application of the mononuclear cobalt complex in electrocatalytic water oxidation, and the mononuclear cobalt complex can be used as a water oxidant in an aqueous solution or an organic solution containing water and used for electrocatalytic oxidation of water to prepare oxygen. The preparation method specifically comprises the steps of dissolving the mononuclear cobalt complex in DMF (dimethyl formamide) and taking an organic electrolyte as a supporting electrolyte; the mononuclear cobalt complex is dissolved in water, and the pH value of the solution is adjusted by phosphoric acid or boric acid, so that the electrocatalytic oxidation of water to prepare oxygen can be realized under a lower overpotential. The mononuclear cobalt complex has the advantages of wide application system and capability of meeting different requirements.
Meanwhile, when the mononuclear cobalt complex is used as a water oxidant in aqueous solution, the mononuclear cobalt complex can work under the condition of pH 3-7. At present, water oxidation under acidic conditions is not achieved by many metal complexes, high concentrations of protons disrupt their structure leading to dissociation, and they do not have sufficient catalytic efficiency even if stably present, because higher proton concentrations are more detrimental to water oxidation.
The prior art is referred to in the art for techniques not mentioned in the present invention.
Drawings
FIG. 1 is a high resolution mass spectrum of a mononuclear cobalt complex according to example 1;
FIG. 2 is a cyclic voltammogram of the mononuclear cobalt complex of example 1 used in the electrocatalytic oxidation of water in DMF solution to oxygen (DMF means dimethylformamide).
FIG. 3 is a cyclic voltammogram of the mononuclear cobalt complex of example 1 used in the electrocatalytic oxidation of water in pure water to produce oxygen.
FIG. 4 is a graph of the oxygen yield of the mononuclear cobalt complexes of example 1 for the electrocatalytic oxidation of water to oxygen.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
0.74mmol of cobalt acetate tetrahydrate (183mg) and 0.74mmol of bipyalk (200mg) (the molar ratio is 1:1) are dissolved in 30mL of ethanol, the mixture is heated to 50 ℃ in a light-shielding environment, reflux and stirring are carried out for reaction for 6 hours, after the reaction is finished, the mixture is taken out and evaporated to the residual 3mL, 5mL of n-hexane is added, and crystallization is carried out at-40 ℃ in a light-shielding environment to obtain the mononuclear cobalt complex, wherein the yield is 82%.
Subjecting the mononuclear cobalt complex to high resolution mass spectrometry (ESI-MS (CH)3OH) see FIG. 1) M/z 330.07663[ M-2OAc ]]2+。
Example 2
1.09mmol of cobalt acetate tetrahydrate (272mg) and 0.90mmol of bipyalk (246mg) (the molar ratio is 11:9) are dissolved in 30mL of ethanol, the mixture is heated to 50 ℃ in a dark environment and stirred under reflux for 6 hours for reaction, after the reaction is finished, the mixture is taken out and evaporated to the residual 4mL, 6mL of n-hexane is added, and the mixture is crystallized at minus 45 ℃ in a dark environment to obtain a mononuclear cobalt complex, the yield is 95%, and the mass spectrum of the obtained product is completely consistent with that of example 1.
Application test 1
The mononuclear cobalt complex prepared in the above example 1 was used for preparing oxygen by electrocatalytic oxidation of water, and the test method was: 25 mu mol of monoAddition of the Nuclear cobalt Complex to 0.1M Bu4NPF6(50mL) in DMF solution, an electrochemical workstation is used for carrying out an electro-catalytic water oxidation test (cyclic voltammetry test) under a three-electrode system (a platinum electrode is used as a counter electrode, a silver-silver chloride electrode is used as a reference electrode, a glassy carbon electrode is used as a working electrode), CV test results are shown in figure 2, Bu4NPF6Is tetrabutylammonium hexafluorophosphate and DMF is dimethylformamide.
As can be seen from FIG. 2, after water is added, the catalytic current is obviously enhanced, the intensity is enhanced by 10-20 times, and the mononuclear cobalt complex has the activity of electrocatalytic water oxidation oxygen generation.
Application test 2
The mononuclear cobalt complex prepared in the above example 1 was used for preparing oxygen by electrocatalytic oxidation of water, and the test method was: adding 25 mu mol of mononuclear cobalt complex into water (50mL), adjusting the pH value of the mixed solution by using phosphoric acid to ensure that the pH values of the solutions are 3, 4, 5, 6 and 7 respectively, carrying out electrocatalytic water oxidation tests (cyclic voltammetry test CV and control potential electrolysis CPE) by using an electrochemical workstation under a three-electrode system (a platinum electrode is a counter electrode, a silver-silver chloride electrode is a reference electrode, and a glassy carbon electrode is a working electrode), and quantitatively analyzing the oxygen generated by the reaction through gas chromatography, wherein the test results are shown in figure 3 and figure 4.
As can be seen from FIG. 3, the electrocatalytic effect of the mononuclear cobalt complex in the pure water system is better than that of the organic system, the catalytic current can reach hundreds of times of that of the mononuclear cobalt complex without the complex, the overpotential is very low, and the mononuclear cobalt complex is calculated to be only 360mV at pH 6 and only 390mV at pH 7. Further, as can be seen from FIG. 4, the oxygen production amount reached 32. mu. mol in 1 hour, and the TON (number of conversions: moles of conversion of reactant/moles of catalyst) reached 5 in one hour.
Comparative example 1
The CoH is prepared using the documents Dilek.Doguttan, Robert McGuire, Jr., and Daniel G.Nocera.Electrocatalytic Water Oxidation by Cobalt (III) Handman β -Octafluoro Corroles.J.am.Chem.Soc.2011,133, 9178-9180βFCX-CO2H(HβFCX ═ β -octafluoro hangmancorrol), and then CoH was added theretoβFCX-CO2H was plated on FTO surface using Nafion in a pure water system, pH was adjusted to 7 with phosphoric acid, catalytic current was only 1/4 for the mononuclear cobalt complexes of the present application at 1.4V (vs silver chloride electrode), and overpotential was as high as 600 mV. In comparative example 1, when the reaction system was adjusted to be acidic, no oxygen generation was detected at 1.4V.
Comparative example 2
Co is prepared using the documents Dong Wang and John T.G. group. effective water oxidation catalysis of by homology proteins with crystalline acids for the buffer base, Proc.Natl.Acad.Sci.U.S.A.2013, 110,15579-15584IITDMImP (TDMImP is 5,10,15, 20-tetra- (1, 3-dimethylimidazol-2-yl) porphyrin), mixing Co with CoIITDMImP was placed in a pure water system, adjusted to pH 7 with phosphoric acid, at a concentration twice that of application example 2, and at 1.4V (relative to a silver-silver chloride electrode) the catalytic current was only 1/8-1/9 for the mononuclear cobalt complexes of the present application, and the overpotential was 580 mV. In comparative example 2, when the reaction system was adjusted to be acidic, no oxygen generation was detected at 1.4V.
Because water oxidation is a deprotonation reaction, the higher the proton concentration is, the more unfavorable the water oxidation is, therefore, under the acidic condition, the difficulty of the water oxidation is increased, and the water oxidation tends to be more difficult along with the enhancement of the acidity.
Claims (8)
1. A mononuclear cobalt complex characterized by: the chemical formula is Co (bipyalk) and (OAc)2The structural formula is as follows:
2. the method for preparing the mononuclear cobalt complex as claimed in claim 1, wherein the mononuclear cobalt complex is obtained by dissolving cobalt acetate tetrahydrate and bipyalk in ethanol, stirring and reacting for 6-7 hours at 50-60 ℃ in a dark environment, taking out and carrying out rotary evaporation, adding n-hexane, and crystallizing at-40 to-50 ℃ in a dark environment.
3. The method of claim 2, wherein the molar ratio of cobalt acetate tetrahydrate to bipyalk is 1.0 to 1.4: 1.
4. the preparation method according to claim 2, wherein the molar ratio of ethanol to bipyalk is 500-700: 1.
5. the method according to claim 2, wherein the molar ratio of n-hexane to bipyalk is 40 to 60: 1.
6. use of the mononuclear cobalt complex according to claim 1 as an oxidation agent for water in electrocatalytic oxidation of water, characterized in that the mononuclear cobalt complex is capable of acting as an oxidation agent for water in aqueous or water-containing organic solution.
7. Use according to claim 6, wherein the aqueous solution has a pH of 3 to 7.
8. Use according to claim 7, characterized in that the pH of the aqueous solution is adjusted with phosphoric acid or boric acid.
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| Title |
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| N,N,O Pincer Ligand with a Deprotonatable Site That Promotes Redox-Leveling, High Mn Oxidation States, and a Mn2O2 Dimer Competent for Catalytic Oxygen Evolution;Hannah M. C. Lant et al.;《Oxygen Evolution Catalysis》;20190114;第2115-2123页 * |
| Synthesis, characterization, and electrochemical behavior of a cobalt(II) salen-like complex;Ali Ourari et al.;《Polyhedron》;20150522;第197-201页 * |
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