Fe-N-C catalyst, method of preparation and uses thereof

A technology of application and catalytic material, applied in the field of catalysts for CO2 electroreduction, can solve the problems of low partial current density and low CO generation rate, and achieve the effect of reducing production costs and avoiding regeneration requirements.

Pending Publication Date: 2020-09-29
加兹纳特股份公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Catalysts containing earth-abundant metals such as iron, cobalt, and nickel have been developed, but their partial current densities are still lower than those based on gold and silver
In particular, using commercially available zeolitic imidazole framework (ZIF), ZIF-8, iron(II) acetate (Fe(Ac) 2 ) and phenanthroline (phen) as precursors, which were mixed by ball milling before pyrolysis, produced catalytic materials with various properties, but all achieved a CO generation rate much lower than that of the gold catalyst, that is, at -0.4V About 2mA·cm -2 (Huan et al., 2017, ACS Catal., 7, 1520)

Method used

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  • Fe-N-C catalyst, method of preparation and uses thereof
  • Fe-N-C catalyst, method of preparation and uses thereof
  • Fe-N-C catalyst, method of preparation and uses thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0107] Embodiment 1: the preparation of the Zn-ZIF precursor of Fe (II) doping

[0108] The inventive method for preparing Fe(II)-doped Zn-zeolite imidazole frameworks (ZIFs) according to the invention is as Figure 1B shown for Fe(II)-doped zinc imidazole (ZIF-8). In order to prevent the oxidation of Fe(II) species during the reaction, before use by bubbling N 2 The reaction medium, i.e. methanol (MeOH) or ethanol, was degassed, and the Fe(II)-doped Zn-ZIF-8 material was synthesized in a glove box as follows:

[0109] The imidazolate precursor is provided to prepare Solution A:

[0110] First, 1.314 g of 2-methylimidazole (2-mIm) was provided as an imidazolate precursor, and 0.076 g of potassium iodide (KI) was dissolved in 15 mL of MeOH to form solution A.

[0111] Iron(II) chloride is supplied to prepare solution B:

[0112] 0.080 g FeCl 2 4H 2 O or 0.063 g FeCl 2 As Fe(II) precursor and 1.190 g Zn(NO 3 ) 2 ·6H 2 O was dissolved in 25 mL of MeOH to form solution B...

Embodiment 2

[0117] Embodiment 2: prepare catalytic material of the present invention by Fe (II) doped Zn-ZIF

[0118] exist Figure 1A The inventive process for the preparation of catalysts comprising Fe single atoms on N-doped carbon substrates obtained from Fe(II)-doped Zn-ZIFs according to the invention is described in , using the Fe obtained in Example 1 (II) Doped zinc imidazolium (ZIF-8) as a precursor for pyrolysis. During the transfer from the glove box to the tube furnace, the Fe(II)-doped zinc imidazolium (ZIF-8) precursor obtained in Example 1 was immersed in hexane to prevent possible exposure to air. oxidation. Then in a tube furnace at 900 °C at 100 mL min -1 N 2 Pyrolysis was carried out for 3 hours at the flow rate, and the heating rate was 5°C·min -1 . Catalytic material obtained by pyrolysis as black powder. The obtained yield was about 90% based on Fe.

Embodiment 3

[0119] Example 3: Characterization of Fe(II)-doped zinc imidazole (ZIF-8) precursor and its pyrolysis products

[0120] Such as figure 2 As reported on a, compared with the same method as in Example 1 in the absence of FeCl 2 or FeCl 2 4H 2 X-ray diffraction (XRD) patterns of undoped ZIF-8 and the Fe(II)-doped zinc imidazolium (ZIF-8) precursor of the present invention prepared in the presence of O. Such as figure 2 b, comparing the XRD patterns of the material obtained after pyrolysis of undoped ZIF-8 and Fe(II)-doped ZIF-8.

[0121] To prepare samples for XRD characterization, the material in solid form was first dispersed in a small amount of ethanol, dropped on a glass slide, and then dried naturally. XRD measurements on an XPert with monochromatic Cu Kα radiation and a fast Si-PIN multiband detector TM performed on a Philips diffractometer.

[0122] Such as figure 2 As shown in a, undoped ZIF-8 (top) and Fe(II)-doped ZIF-8 (bottom) have similar X-ray diffraction (...

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Abstract

The invention relates to single-atom Fe catalysts useful for the electrochemical reduction of carbon dioxide, method of preparation as uses thereof. In particular, the invention relates to a method ofpreparation of Fe(II) doped Zn-ZIF precursor material and use thereof in the preparation of a catalyst containing Fe single atoms on N doped carbon matrix derived from the pyrolysis of this Fe(II) doped Zn-ZIF precursor material.

Description

[0001] field of invention [0002] The present invention relates generally to the field of electrochemical reduction of carbon dioxide, in particular for CO 2 Catalyst for electroreduction. Background technique [0003] Atmospheric carbon dioxide (CO 2 ) levels have attracted global attention and foresee a range of environmental consequences, including devastating climate change, that could affect modern civilization. Due to the CO produced in the last fifty years 2 The number of is considerable, so various methods are needed to reduce their number. Among them, the CO 2 Electrochemical reduction methods to useful chemical species include carbon monoxide (CO), formic acid, methane, and ethylene (Jhong et al., 2013, Modern Perspectives in Chemical Engineering, 2(2), 191-199). [0004] Therefore, the CO in the aqueous electrolyte 2 Electrolytic reduction to CO is considered to convert CO 2 and electricity into CO and O 2 A promising technique for its fixation of CO 2 , w...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01B37/00B01J21/18C01B39/00C25B3/04C01B32/05C25B3/25
CPCC01B32/05C01B37/00C01B39/00C25B1/00C25B11/091C01B32/40B01J29/048B01J37/082
Inventor 胡喜乐顾均
Owner 加兹纳特股份公司
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