Boron-doped copper catalysts for efficient conversion of CO2 to multi-carbon hydrocarbons and associated methods

Patent metadata

Field	Value
Publication number	US-11390959-B2
Application number	US-201917049740-A
Country	US
Kind code	B2
Filing date	Apr 23, 2019
Priority date	Apr 24, 2018
Publication date	Jul 19, 2022
Grant date	Jul 19, 2022

Abstract

The invention relates to a catalyst system for catalyzing conversion of carbon dioxide into multi-carbon compounds comprising a boron-doped copper catalytic material and associated methods.

First claim

The invention claimed is:

1. A catalyst system for catalyzing conversion of carbon dioxide (CO 2 ) into multi-carbon compounds, the catalyst system characterized in that the catalyst system comprises a boron-doped copper catalytic material, wherein the boron-doped copper catalytic material has a boron concentration that decreases with depth into the material, and further wherein the boron-doped copper catalytic material has a boron concentration of about 4-7 mol % proximate at the external surface of the catalyst and has a boron concentration below about 4 mol % beyond a depth of about 7 nm from the external surface; the boron concentration determined by Inductively coupled plasma optical emission spectrometry.

2. The catalyst system of claim 1 , characterized in that the boron-doped copper catalytic material has a porous dendritic morphology.

3. The catalyst system of claim 1 , characterized in that the boron-doped copper catalytic material has a particle size ranging from 30 to 40 nm as determined by scanning electron microscopy.

4. The catalyst system of claim 1 , characterized in that the copper comprises Cu (111).

5. The catalyst system of claim 1 , characterized in that the catalyst system further comprises:
a gas-diffusion layer; and
a catalyst layer comprising the boron-doped copper catalytic material applied to the gas-diffusion layer.

6. A method for electrochemical production of a multi-carbon hydrocarbon product, comprising:
contacting CO 2 gas and an electrolyte with an electrode comprising the catalyst system as defined in claim 5 , the catalyst system comprising a catalyst layer comprising the boron-doped copper catalytic material, and a gas-diffusion layer, wherein the gas-diffusion layer, when present, is arranged in such a way that the CO 2 gas diffuses through the gas-diffusion layer and contacts the catalyst layer, preferably, the gas-diffusion layer is hydrophobic;
applying a voltage to provide a current density to cause the CO 2 gas contacting the catalyst layer to be electrochemically converted into the multi-carbon hydrocarbon product; and
recovering the multi-carbon hydrocarbon product.

7. The method of claim 6 , wherein the electrolyte comprises an alkaline potassium compound.

8. A method to produce the boron-doped copper catalytic material for a catalyst system according to claim 1 , characterized in that the copper comprises Cu (111); and in that the boron-doped copper catalytic material is prepared via incipient wetness impregnation of a single crystal Cu (111) material with a boric acid aqueous solution.

9. The method of claim 8 , characterized in that the impregnation step is followed by a calcination step.

10. The method of claim 8 , characterized in that the doped metal catalytic material has a boron concentration ranging from 4 to 7 mol % at the external surface of the catalyst, and has a boron concentration below about 4 mol % beyond a depth of about 7 nm from the external surface, the boron concentration is determined by Inductively coupled plasma optical emission spectrometry.

11. A method of manufacturing a boron doped copper catalytic material for a catalyst system according to claim 1 , in order to perform CO 2 reduction; the method being characterized in that the comprises a step of combining copper chloride (CuCl 2 ) with borohydride in solution to form catalyst precipitates in the solution and a step of recovering the catalyst precipitates from the solution; wherein the concentration in solution of the borohydride is ranging from 3 to 6 M, and wherein the concentration in solution of the CuCl 2 is ranging from 40 to 400 mg/m.

12. The method of claim 11 , characterized in that the catalyst precipitates recovered from the solution are subjected to a drying step to form dried catalyst precipitates.

13. The method of claim 11 , characterized in that the concentration in solution:
of the borohydride is ranging from 4 to 5 M; or,
of the CuCl 2 is ranging from 80 to 200 mg/mL.

14. The method of claim 11 , characterized in that the solutions of CuCl 2 and a solution of the borohydride are provided in volume ratios ranging from 10:1 to 1:10.

Assignees

• Total Se
• Governing Council Univ Toronto

Inventors

• Sargent Edward
• De Luna Phil
• Che Fanglin
• Zhou Yansong

Classifications

• C25B11/091 Primary

  consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds · CPC title

• H01M4/9091

  Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state · CPC title

• C30B29/02

  Elements · CPC title

• H01M4/9041 Primary

  Metals or alloys (H01M4/92 takes precedence) · CPC title

• C30B31/04

  by contacting with diffusion materials in the liquid state · CPC title