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A kind of nanomaterial co-assembled with heme and pyridyl metalloporphyrin, its preparation method and application

A nano-material and metal-based technology, applied in the field of material chemistry and electrochemical catalysis, can solve the problems of difficult to expose active sites, unable to form controllable and orderly regulated bimetallic ratio, bimetallic spacing, etc.

Active Publication Date: 2021-07-13
HENAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the current methods for preparing metal-doped graphitized carbon materials are disadvantageous in that the metal active sites of the obtained electrocatalytic materials are aggregated and oxides are produced, it is difficult to expose more active sites, and it is impossible to form a controllable and ordered Adjust the ratio of bimetallic, bimetallic spacing

Method used

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  • A kind of nanomaterial co-assembled with heme and pyridyl metalloporphyrin, its preparation method and application
  • A kind of nanomaterial co-assembled with heme and pyridyl metalloporphyrin, its preparation method and application
  • A kind of nanomaterial co-assembled with heme and pyridyl metalloporphyrin, its preparation method and application

Examples

Experimental program
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Effect test

Embodiment 1

[0033] A method for preparing Fe / M metal-doped graphitized carbon materials based on heme and pyridyl metalloporphyrin co-assembled nanomaterials, comprising the following steps:

[0034] (1) Prepare the NaOH solution of heme (referred to as Hemin / NaOH solution), the concentration of Hemin in NaOH solution is 0.01 mol / L, and the solubility of NaOH solution is 0.02 mol / L, and keep stirring at 25°C for 40 -45 min standby;

[0035] (2) Prepare the HCl solution of pyridyl metal cobalt porphyrin (CoTPyP) (denoted as CoTPyP / HCl solution), the concentration of MTPyP in the HCl solution is 0.01 mol / L, and the solubility of the HCl solution is 0.02 mol / L, and Stir continuously at 25°C for 40-45 min for later use;

[0036] (3) Prepare a mixed solution of CTAB and NaOH solution, dissolve CTAB in water, add 38 μL of 1 mol / L NaOH solution, so that the volume of the solution is 9.5 mL and the concentration of CTAB in the solution is 0.01 mol / L;

[0037] (4) Take 100 μL of step 1) and 400 ...

Embodiment 2

[0043] A method for preparing Fe / M metal-doped graphitized carbon materials based on heme and pyridyl metalloporphyrin co-assembled nanomaterials, the difference from Example 1 is that: take 200 μL step 1) and 300 μL respectively 2) The solution was quickly injected into the step 3) containing different volumes of 1 mol / L NaOH or 1 mol / L HCl solution, respectively containing 210 μL HCl, 80 μL HCl, 17 μL HCl, 6.90 μL NaOH, 9.05 μL NaOH, 9.92 μL NaOH solution, the pH values ​​of the mixed solution were finally measured to be about 1.7, 2.2, 2.7, 3.7, 4.7, and 5.2 respectively. Stirring was continued for 48 hours at 25°C, and centrifuged. Assembly ratio (2:3) of Fe / Co co-assembled materials with different pH values.

[0044] Different pH 1.7 ( image 3 A), 2.2 ( image 3 B), 2.7 ( image 3 C), 3.7 ( image 3 D), 4.7 ( image 3 E), 5.2 ( image 3 F), the SEM image of the co-assembly obtained under the same raw material ratio (2:3) image 3 As shown, it can be seen that as t...

Embodiment 3

[0046] A method for preparing Fe / M metal-doped graphitized carbon materials based on heme and pyridyl metalloporphyrin co-assembled nanomaterials, the difference from Example 1 is that 0.01 mol / L in (2) Replace CoTPyP / HCl solution with 0.01 mol / L ZnTPyP / HCl solution, take 250 μL (2) solution and 250 μL (1) solution respectively, and quickly inject them into 9.5 mL step 3) at the same time, and finally measure the pH value of the mixed solution is about 3.6, and a Fe / Zn co-assembled material with a self-assembly ratio of (1:1) is obtained. Then heat treatment according to Example 1, obtain the Fe / Zn double-doped graphitized carbon material with a carbon formation rate of 40%; Single-heterographitized carbon material; CoTPyP powder, the raw material for assembly, was heat-treated according to Example 1 to obtain a Co mono-heterographitized carbon material with a carbonization rate of 24%.

[0047] Such as Figure 4 as shown, Figure 4 As seen in A, the morphology of the Fe / Zn...

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Abstract

The invention discloses a co-assembled nanomaterial of heme and pyridyl metalloporphyrin, its preparation method and application, and belongs to the technical field of material chemistry and electrochemical catalysis. Pyridyl metalloporphyrin co-assembled nanomaterials, by adjusting the feeding ratio of heme and pyridyl metalloporphyrin, the pH value of the reaction solution, the central metal of pyridyl porphyrin, and other conditions to obtain co-assemblies with different shapes, in a protective atmosphere calcination at high temperature and down to room temperature to obtain Fe / M doped graphitized carbon material. The present invention utilizes that heme contains two carboxyl groups, so that it can be dissolved in NaOH solution to generate anion. Since tetrapyridyl metalloporphyrin itself contains four pyridine groups, it can be dissolved in HCl and protonated to generate cation. The interaction force between the two porphyrins makes better assembly, which greatly increases the solubility of the reactants, thereby increasing the yield of the product.

Description

technical field [0001] The invention belongs to the field of material chemistry and electrochemical catalysis, and specifically relates to a co-assembled nanomaterial of heme and pyridyl metalloporphyrin, its preparation method and application. Background technique [0002] With the advancement of science and technology, the pollution of the environment by fossil fuels and the depletion of energy, more and more environmental and energy issues have attracted everyone's close attention. In today's society, people cannot travel without cars, and the environmental pollution caused by automobile gas cannot be ignored. The development of fuel vehicles with high battery life and low pollution is a key choice for the sustainable development of human beings and the improvement of the quality of human life. However, due to kinetic limitations, the fuel cell cathode oxygen reduction reaction (ORR) reaction is slow, which is the speed-controlling step of fuel cells, which restricts the ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/90H01M4/88B82Y30/00
CPCB82Y30/00H01M4/8828H01M4/9041H01M4/9083Y02E60/50
Inventor 钟永张文志白锋任希彤田甜鲍建帅
Owner HENAN UNIVERSITY
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