Upgrading of co to c3 products using multi-metallic electroreduction catalysts with assymetric active sites

Abstract

The present disclosure relates to electrocatalysts for electroreduction of a carbon-containing gas to produce n-propanol, for example. The electrocatalyst includes a multi-metallic material comprising a primary metal, such as Cu, and a metal dopant, such as Ag, selected and distributed to provide asymmetric active sites that include neighbouring atoms of the primary metal having distinct electronic structures to promote C2-C1 coupling. The electrocatalysts can be bimetallic or bimetallic, for example. The disclosure also relates to manufacturing and using the electrocatalysts, which can be used as a cathodic catalyst to convert CO or CO2 into multi-carbon products.

1 . An electrocatalyst for electroreduction of a carbon-containing gas to produce C3 products, the electrocatalyst comprising a multi-metallic material comprising a primary metal and a metal dopant selected and distributed to provide asymmetric active sites that include neighbouring atoms of the primary metal having distinct electronic structures to promote C2-C1 coupling. 
     
     
         2 . The electrocatalyst of  claim 1 , wherein the primary metal is Cu. 
     
     
         3 . The electrocatalyst of  claim 2 , wherein the metal dopant is Ag and the multi-metallic material is a bimetallic material. 
     
     
         4 . The electrocatalyst of  claim 1 , wherein the metal dopant comprises Ag and a second dopant metal and the multi-metallic material is a trimetallic material. 
     
     
         5 - 7 . (canceled) 
     
     
         8 . The electrocatalyst of  claim 1 , wherein the C3 product is n-propanol. 
     
     
         9 . The electrocatalyst of  claim 1 , wherein the multi-metallic material comprises the primary metal doped with the metal dopant using galvanic replacement. 
     
     
         10 . The electrocatalyst of  claim 1 , wherein the metal dopant is present in the primary metal in a doping concentration of 2 wt % to 9 wt %, measured with XPS. 
     
     
         11 . (canceled) 
     
     
         12 . The electrocatalyst of  claim 1 , wherein the metal dopant is present in the primary metal in a doping concentration of 3wt % to 5 wt %, measured with XPS. 
     
     
         13 - 14  (canceled) 
     
     
         15 . The electrocatalyst of  claim 1 , wherein the electrocatalyst is provided in the form of bimetallic or trimetallic nanoparticles. 
     
     
         16 . The electrocatalyst of  claim 15 , wherein the bimetallic or trimetallic nanoparticles have an average size between about 20 nm and about 200 nm, measured based on SEM or TM imaging. Claims  17 - 18  (canceled) 
     
     
         19 . The electrocatalyst of  claim 16 , wherein the bimetallic or trimetallic nanoparticles are generally spheroid in shape, determined from SEM or TM imaging. 
     
     
         20 . The electrocatalyst of  claim 1 , wherein the electrocatalyst is formed as a deposited catalyst layer on a first side of gas diffusion membrane, wherein the deposited catalyst layer is configured to be in direct contact with an electrolyte and wherein a second opposed side of the gas diffusion membrane is configured to be in direct contact with the carbon-containing gas. 
     
     
         21 . An electrocatalyst for electroreduction of a carbon-containing gas to produce a C3 product, the electrocatalyst comprising a bimetallic or trimetallic material comprising a copper (Cu) and at least one metal dopant in a doping concentration of 2 wt % to 9 wt %, measured with XPS. 
     
     
         22 . (canceled) 
     
     
         23 . The electrocatalyst of  claim 21 , wherein the metal dopant comprises a primary dopant and a secondary dopant. 
     
     
         24 . The electrocatalyst of  claim 23 , wherein the primary dopant is Ag. 
     
     
         25 . The electrocatalyst of  claim 24 , wherein the secondary dopant is Ru. 
     
     
         26 - 37 . (canceled) 
     
     
         38 . A method of fabricating an electrocatalyst composed of a primary metal and at least one metal dopant for electroreduction of a carbon containing gas into C3 products, such as n-propanol, comprising galvanic replacement, wherein the electrocatalyst is as defined in  claim 1 . 
     
     
         39 . The method of  claim 38 , comprising:
 providing a layer of Cu particles on a substrate to provide a coated substrate;   immersing the coated substrate in an Ag containing aqueous solution to induce doping and form an Ag-doped multimetallic catalyst material supported by the substrate; and   removing the coated substrate from the solution, the coated substrate comprising a layer of the Ag-doped multimetallic catalyst material.   
     
     
         40 - 44 . (canceled) 
     
     
         45 . A process for electrochemical production of a C3 multi-carbon compound from a carbon-containing gas, comprising:
 contacting the carbon-containing gas and an electrolyte with an electrode comprising the electrocatalyst as defined in  claim 1 , such that the carbon-containing gas contacts the electrocatalyst;   applying a voltage to provide a current density to cause the carbon-containing gas contacting the electrocatalyst to be electrochemically converted into the C3 multi-carbon compound; and   recovering the C3 multi-carbon compound.   
     
     
         46 - 47 . (canceled) 
     
     
         48 . The process of  claim 45 , wherein the C3 multi-carbon compound is n-propanol. 
     
     
         49 . (canceled) 
     
     
         50 . The process of  claim 45 , wherein the electrolyte comprises KOH. 
     
     
         51 . The process of  claim 45 , wherein the carbon-containing gas comprises CO. 
     
     
         52 . The process of  claim 45 , wherein the carbon-containing gas comprises CO 2 . 
     
     
         53 . (canceled) 
     
     
         54 . A system for CO and/or CO 2  electroreduction to produce a multi-carbon compound, comprising:
 an electrolytic cell configured to receive a liquid electrolyte and CO and/or CO 2  gas;   an anode;   a cathode comprising an electrocatalyst as defined in  claim 1 ; and   a voltage source to provide a current density to cause the CO and/or CO 2  gas contacting the electrocatalyst to be electrochemically converted into the multi-carbon compound.   
     
     
         55 . (canceled)