Copper porphyrin complex for electro-catalysis oxygen evolution reaction and preparation method of copper porphyrin complex

A technology for oxygen evolution reaction and complexes, which is applied in the directions of organic chemistry methods, chemical instruments and methods, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems such as the application of unreported porphyrin-copper complexes, and achieves The effect of high yield, energy saving and simple reaction conditions

Inactive Publication Date: 2017-09-01
CHINA UNIV OF PETROLEUM (EAST CHINA)
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

None of the above-mentioned ligands used in the construction of complexes involves the use of tetracyanophenylporphyrin ligand 5,10,15,20-tetracyanophenylporphyrin (CNTCPP) and copper nitrate trihydrate to construct copper porphyrin Complexes, the application of porphyrin copper complexes in electrocatalytic oxygen evolution has never been reported

Method used

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  • Copper porphyrin complex for electro-catalysis oxygen evolution reaction and preparation method of copper porphyrin complex
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  • Copper porphyrin complex for electro-catalysis oxygen evolution reaction and preparation method of copper porphyrin complex

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Embodiment 1

[0030] Embodiment 1: This embodiment relates to the preparation of porphyrin copper complex:

[0031] (1) The reactants 5,10,15,20-tetracyanophenylporphyrin (CNTCPP) and copper nitrate trihydrate are fed in a molar ratio of 1:5. Accurately weigh 0.02g, 0.028mmol of 5,10,15,20-tetracyanophenylporphyrin (CNTCPP) and 0.034g, 0.14mmol of copper nitrate trihydrate in the reaction vessel with an analytical balance; at room temperature, add 5mL of Water N, N' dimethylformamide solvent was stirred for 12 hours, the reaction was stopped, and the reaction solution was filtered with filter paper to obtain a blue-green filtrate;

[0032] (2) Add HBF to the filtrate 4 The pH value of the solution was adjusted to 6, and then the filtrate was transferred to a 25mL polytetrafluoroethylene-lined stainless steel reactor, and then placed in a constant temperature blower box at 85°C for 1000 minutes to obtain light blue crystals.

[0033]Elemental analysis theoretical value: C, 70.31; H, 4.15; ...

Embodiment 2

[0045] Embodiment 2: This embodiment involves complex electrocatalytic oxygen evolution reaction:

[0046] In order to study the oxygen evolution performance of the material, a three-electrode system was used to test on an electrochemical workstation (Gamry Reference600 Instruments, USA). Disperse 5.0 mg of the porphyrin copper complex prepared in Example 1 as a catalyst and 20.0 μL of Nafion (5 wt%) solution in 1 mL of ethanol-water mixed solution (volume ratio of ethanol: water is 1:1), and ultrasonically treat for 1 hour to obtain Uniform dispersion. Then 5.0 μL of this dispersion was loaded on a glassy carbon electrode with a diameter of 4 mm. Use 1.0M KOH as the electrolyte (bubble pure oxygen for 30 minutes to remove dissolved oxygen), a saturated calomel electrode as a reference electrode, a high-purity platinum electrode as a counter electrode, and a glassy carbon electrode loaded with a catalyst as a working electrode. the s -1 The scan rate was used to measure the...

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Abstract

The invention discloses a copper porphyrin complex for electro-catalysis oxygen evolution reaction and a preparation method of the copper porphyrin complex, and in particular discloses a metal-organic complex which is concise, efficient and green at relatively low temperature and is prepared on the basis of a 5,10,15,20-tert-cyan phenyl porphyrin organic ligand, a preparation method, and application of the complex in electro-catalysis oxygen evolution reaction. The 5,10,15,20-tert-cyan phenyl porphyrin organic ligand and copper nitrate trihydrate are adopted as raw materials, the chemical formula of the obtained copper porphyrin complex is [C108Cu2N20O4H0.25], the complex belongs to a monoclinic system and a space group of P2 / a, the cell parameters includes the axial length a being 15.3680(2) angstroms, b being 17.1634(2) angstroms, c being 33.5945(6) angstroms, the axial angle alpha being 90.00 degrees, beta being 93.8488(13) degrees, and gamma being 90.00 degrees, and the unit cell volume V is 8841.2(2) angstrom 3. The copper porphyrin complex disclosed by the invention is good in catalysis property in the electro-catalysis oxygen evolution reaction, the oxygen evolution overpotential of the copper porphyrin complex is 1.66v (vs.RHE is relative to a reversible hydrogen electrode) when the current density is 10mA / cm<2>. The preparation method is simple in process, only organic solvents are used, the copper porphyrin complex can be recycled, and no wastes are discharged.

Description

technical field [0001] The invention belongs to the technical field of new materials, and specifically discloses a simple, high-efficiency, green metal-organic framework material (porphyrin copper complex) constructed on the basis of porphyrin organic ligands at a relatively low temperature, a preparation method and its application in Application in electrocatalytic oxygen evolution reaction. Background technique [0002] Hydrogen energy is considered to be the most potential secondary energy source in the 21st century. Hydrogen production by electrolysis of alkaline water is an important topic in the research and development of hydrogen energy. One of the main reasons for the high energy consumption and low efficiency in the process of water electrolysis is the high oxygen evolution overpotential. If the anode overpotential is too high, the energy conversion efficiency will be low. If an ideal electrocatalytic oxygen evolution anode material with a lower oxygen evolution o...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D487/22B01J31/22C25B1/04C25B11/06
CPCB01J31/183B01J35/0033B01J2531/025B01J2531/16C07B2200/13C07D487/22C25B1/04C25B11/04Y02E60/36
Inventor 戴昉纳范卫东王雨桐袁雪黄招娣林欢张明会
Owner CHINA UNIV OF PETROLEUM (EAST CHINA)
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