Copper-cobalt-zinc composite self-supporting nano array electrode material and preparation method and application thereof

An electrode material and nano-array technology, which is applied in the field of copper-cobalt-zinc composite self-supporting nano-array electrode material and its preparation, can solve the problems of inherent energy barrier and slow electron transfer, limited reserve hindering, increasing interface resistance, etc. Electrochemical reactivity, green reaction, and the effect of reducing interface resistance

Active Publication Date: 2021-06-11
TIANJIN POLYTECHNIC UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, both reactions suffer from inherent energy barriers and slow electron transfer
[0003] Among the electrocatalysts for water electrolysis, Ir / Ru-based and Pt-based commercial noble metal catalysts for catalyzing OER reactions are mainly used, but the high cost and limited reserves of these noble metal catalysts seriously hinder large-scale applications.
In addition, powder electrocatalysts usually use polymer binders to immobilize active materials to prepare electrodes, and polymer binders not only block active sites but also increase interfacial resistance.
Literature "Z.Chen, Y.Ha, H.Jia, X.Yan, M.Chen, M.Liu, R.Wu, Oriented Transformation of Co-LDH into 2D / 3D ZIF-67to Achieve Co-N-C Hybrids for Efficient Overall Water Splitting, Adv.Energy Mater.9(2019) 1803918" uses Co hydroxide to self-support and synthesize high-efficiency electrolytic water catalyst on carbon fiber, but carbon fiber as a self-supporting body inevitably encounters complex pre-treatment and poor stability And other issues

Method used

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  • Copper-cobalt-zinc composite self-supporting nano array electrode material and preparation method and application thereof
  • Copper-cobalt-zinc composite self-supporting nano array electrode material and preparation method and application thereof
  • Copper-cobalt-zinc composite self-supporting nano array electrode material and preparation method and application thereof

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preparation example Construction

[0027] The invention provides a method for preparing a copper-cobalt-zinc composite self-supporting nano-array electrode material (method for short), characterized in that the method comprises the following steps:

[0028] Step 1. Oxidize copper to copper hydroxide by oxidation-reduction reaction, then wash and dry to obtain a regular and orderly copper hydroxide nanowire array structure (referred to as a wire array structure);

[0029] Preferably, in step 1, the copper is copper foam (CF).

[0030] Preferably, in step 1, the oxidation-reduction reaction is to soak the copper into the oxidation-reduction agent until the solid matter changes from copper yellow to blue.

[0031] Preferably, the redox agent is NaOH and (NH 4 ) 2 S 2 o 8 Aqueous solution of NaOH and (NH 4 ) 2 S 2 o 8 The mol ratio is 20:1~5 (preferably 20:1), soaking time is 10~30min (preferably 20min);

[0032] Preferably, in step 1, the washing is to wash with water several times before washing with eth...

Embodiment 1

[0049] Step 1, placing foam copper in 20:1 NaOH and (NH 4 ) 2 S 2 o 8 Soak in the aqueous solution for 20 minutes, oxidize the foamed copper to copper hydroxide by oxidation-reduction reaction, then take it out and wash it with ethanol solution to neutral pH=7, dry it in a vacuum oven at 60°C for 3 hours to obtain a linear array structure;

[0050] Depend on figure 1 It can be seen that the linear array structure obtained in step 1 is uniform and arranged in an orderly manner, with a diameter ranging from 250 to 350 nm and a length of 5 to 10 μm.

[0051] Step 2, the product that step 1 obtains is soaked in containing Co(NO 3 ) 2 ·6H 2 O and Zn(NO 3 ) 2 ·6H 2 O molar ratio is 1h in the methanol solution of 2:8, then is placed in the 2-methylimidazole methanol solution of 0.4M, slowly stirs 30min; The mol ratio of metal ion and 2-methylimidazole is 1:8; Then Take it out and wash it with methanol solution to neutral pH = 7, and dry it in a vacuum oven at 100°C for 8 ho...

Embodiment 2

[0054] Step 1, placing foam copper in 20:1 NaOH and (NH 4 ) 2 S 2 o 8 Soak in the aqueous solution for 20 minutes, oxidize the foamed copper to copper hydroxide by oxidation-reduction reaction, then take it out and wash it with ethanol solution to neutral pH=7, dry it in a vacuum oven at 60°C for 3 hours to obtain a linear array structure;

[0055] Step 2, the product that step 1 obtains is soaked in containing Co(NO 3 ) 2 ·6H 2 O and Zn(NO 3 ) 2 ·6H 2 O molar ratio is the methanol solution of 4:6 1h, then is placed in the 2-methylimidazole methanol solution of 0.4M, slowly stirs 30min; The mol ratio of metal ion and 2-methylimidazole is 1:8; Then Take it out and wash it with methanol solution to neutral pH = 7, and dry it in a vacuum oven at 100°C for 8 hours to obtain a self-supporting structure @ZIF;

[0056] Step 3, the product that step 2 obtains is placed in containing Co(NO 3 ) 2 ·6H 2 O and Zn(NO 3 ) 2 ·6H 2 O in an ethanol solution with a molar ratio of...

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Abstract

The invention discloses a copper-cobalt-zinc composite self-supporting nano array electrode material and a preparation method and application thereof. The method comprises the following steps of oxidizing copper into copper hydroxide, washing and drying to obtain a linear array structure; soaking the linear array structure in a methanol solution containing metal ions, and enabling the metal ions to fully grow on the linear array structure; then placing in a methanol solution of 2-methylimidazole until a solid substance is changed from blue to purple, washing and drying to obtain a self-supporting structure @ZIF, wherein the metal ions are Co ions and Zn ions; and placing the self-supporting structure@ ZIF in an ethanol solution containing Co ions and Zn ions, and carrying out solvothermal reaction in a closed environment until the solid substance becomes gray from purple to obtain the electrode material. The electrode material has a highly ordered hollow nano array, a large number of defect holes exist in the surface of the nano array, more active sites and smooth electron transmission channels are provided for the catalytic process, and the electrode material can be used as a positive electrode and a negative electrode of a water electrolysis device.

Description

technical field [0001] The invention belongs to the field of electrocatalytic total water splitting for hydrogen production, in particular to a copper-cobalt-zinc composite self-supporting nano-array electrode material and its preparation method and application. Background technique [0002] In recent years, hydrogen energy has attracted increasing attention as one of the most promising renewable energy sources to replace traditional fossil energy due to its extraordinary energy density, sustainability, and zero emissions. Therefore, it is necessary and urgent to develop efficient ways to produce pure hydrogen. Electrolyzed water is an ideal choice to solve this requirement. It is to decompose pure water into hydrogen for energy storage through electrochemical methods, including anode oxygen evolution reaction (OER) and cathode hydrogen evolution reaction (HER). . However, both reactions suffer from inherent energy barriers and slow electron transfer. [0003] Among the e...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01G11/86H01G11/36B82Y40/00B82Y30/00
CPCH01G11/36H01G11/86B82Y30/00B82Y40/00Y02P20/133
Inventor 杜玺尹雷雷邸辰泽苏坤梅李振环
Owner TIANJIN POLYTECHNIC UNIV
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