EP4276224A1 - Functionnalised copper electrochemical catalysts for conversion of co2 to small molecules - Google Patents

Functionnalised copper electrochemical catalysts for conversion of co2 to small molecules Download PDF

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Publication number
EP4276224A1
EP4276224A1 EP22305716.7A EP22305716A EP4276224A1 EP 4276224 A1 EP4276224 A1 EP 4276224A1 EP 22305716 A EP22305716 A EP 22305716A EP 4276224 A1 EP4276224 A1 EP 4276224A1
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copper
gas diffusion
group
chosen
process according
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German (de)
French (fr)
Inventor
Damien Voiry
Huali WU
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Centre National de la Recherche Scientifique CNRS
Universite de Montpellier I
Ecole Nationale Superieure de Chimie de Montpellier ENSCM
Universite de Montpellier
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Centre National de la Recherche Scientifique CNRS
Universite de Montpellier I
Ecole Nationale Superieure de Chimie de Montpellier ENSCM
Universite de Montpellier
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Priority to EP22305716.7A priority Critical patent/EP4276224A1/en
Priority to PCT/EP2023/062517 priority patent/WO2023217917A1/en
Publication of EP4276224A1 publication Critical patent/EP4276224A1/en
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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    • C25B3/00—Electrolytic production of organic compounds
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    • C25B3/00—Electrolytic production of organic compounds
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    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50

Definitions

  • the present invention belongs to the field of catalytic chemistry, and more specifically to catalysed reduction chemical reactions, preferably of CO 2 into small molecules.
  • the present invention relates to a new catalyst compound comprising at least a copper (Cu) layer, wherein the copper layer is functionalized with at least one aryl functional group and its use thereof in a reduction chemical reaction, preferably in reduction of CO 2 into CO, ethylene and other small molecules such as gaseous hydrocarbons (methane, propane) or liquid molecules (ethanol, formic acid, propanol).
  • the invention relates to the process of manufacture of said catalyst compound and to a process electrochemical conversion of CO 2 to small molecules and in particular ethylene.
  • CO 2 carbon dioxide
  • CO carbon monoxide
  • HCOOH formic acid
  • methane CH 4
  • methanol CH 3 OH
  • ethanol C 2 H 5 OH
  • ethylene C 2 H 4
  • Applicant has developed a new process and a new catalyst compound that solves all of the problems listed above.
  • the present invention deals with a new process and a new catalyst compound, and its applications, such as a method to convert CO 2 into small molecules, more preferably ethylene, at room temperature and atmospheric pressure. Being able to produce such small molecules at room temperature and atmospheric pressure in large quantities is, to the knowledge of Applicant, something that was not observed in the art.
  • the catalyst compound of the invention is based on copper (Cu) and optionally Ag, Bi, Zn and/or Sn crystal grown on a porous gas diffusion layer (typically a commercial carbon support such as a gas diffusion electrode or a porous polymer substrate such as PTFE, nylon or PVDF) via electrodeposition and then functionalization with various substituted aryl groups.
  • a porous gas diffusion layer typically a commercial carbon support such as a gas diffusion electrode or a porous polymer substrate such as PTFE, nylon or PVDF
  • the catalyst compound obtained by the process of the invention may present a raspberry-like morphology.
  • a first object of the invention is a process of manufacture of a catalyst compound comprising the steps of:
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein X - is chosen from BF 4 - , Cl - and HSO 4 - .
  • aryl a group derived from arenes by removal of a hydrogen atom from a ring carbon atom; arenes being monoyclic and polycyclic aromatic hydrocarbons (IUPAC).
  • aryl groups may comprise from 4 to 10 carbon atoms, preferably 6 carbon atoms.
  • aryl groups Ar A and Ar B do not comprise, heteroatoms besides the heteroatoms comprised in R A , F B and R B .
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein Ar A and/or Ar B are aryl groups comprising 6 carbon atoms and are phenyl groups.
  • Ar A and/or Ar B are phenyl groups substituted by at least one -R A group in ortho, meta and/or para position.
  • the R A substituents when there is more than one R A substituent, the R A substituents may be identical or different from each other and/or when there is more than one R B substituent, the R B substituents may be identical or different from each other.
  • the R A and R B groups may be identical or different.
  • the R A and R B groups may be identical or different.
  • when there are two R A they may both be R 1 , and yet be identical or different (e.g. one may be -Me and the other may be -Et or they may both be -Me).
  • one R A substituent and one R B substituent when one R A substituent and one R B substituent are both R 1 , they may be identical or different (e.g. one may be -Me and the other may be -Et or they may both be -Me).
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R A is a halo group, preferably chosen from Br, Cl and I.
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R A is -NO 2 .
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R A is -R 1 , preferably chosen from - Me, -Et and -Pr (Pr being either isopropyl or n-propyl).
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R A is -OR 1 , preferably chosen from - OMe, -OEt and -OPr (Pr being either isopropyl or n-propyl).
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R A is -NR 2 R 3 , preferably chosen from -NEt 2 , -NMe 2 , -NPr 2 , -NMeEt and -NMePr (Pr being either isopropyl or n-propyl).
  • the diazonium salt may be chosen from diazonium salt of formula I, wherein at least one R A group is a group of formula II.
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R B is a halo group, preferably chosen from Br, Cl and I.
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R B is -NO 2 .
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R B is -R 1 , preferably chosen from - Me, -Et and -Pr (Pr being either isopropyl or n-propyl).
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R B is -OR 1 , preferably chosen from - OMe, -OEt and -OPr (Pr being either isopropyl or n-propyl).
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R B is -NR 2 R 3 , preferably chosen from -NEt 2 , -NMe 2 , -NPr 2 , -NMeEt and -NMePr (Pr being either isopropyl or n-propyl).
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R A group is a group of formula II and Ar A and Ar B are each substituted by one -R 1 group, preferably -Me.
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R A group is a group of formula II and Ar A is substituted by two - OR 1 groups, preferably -OMe and Ar B is substituted by one -NO 2 group.
  • the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one R A group is a group of formula II and Ar B is substituted by one - OR 1 group, preferably -OMe.
  • the diazonium salt may be chosen from the following salts: Table 1: example of salts Salts names (IUPAC) Diazonium X - 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazoniu m 4-[(4-methoxyphenyl)amino]benzene-1-diazonium chloride Cl - dichlorozinc;2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl]benzenediazonium; dichloride Cl - .
  • diazonium salt of formula I may be chosen from the following salts:
  • step a) and/or step b) of the process according to the invention may be conducted using a potentiostat.
  • the porous gas diffusion layer may be a commercial conducting carbon-based gas diffusion electrode or a porous polymer substrate such as (PTFE, nylon, PVDF).
  • step a) and/or step b) of the process according to the invention may be conducted under a current density from 5 mA.cm -2 to 50 mA.cm -2 , preferably from 10 mA.cm -2 to 20 mA.cm -2 , and more preferably at 15 mA.cm -2 .
  • the quantity of deposited Cu may be from 0.5 C.cm -2 to 50 C.cm -2 , preferably between 15 C.cm -2 to 35 C.cm -2 , more preferably at 15 mA.cm -2 .
  • step a) and/or step b) of the process according to the invention may be done under pulse deposition or galvanostatic method.
  • the applied current density for electrodepositing copper is 15 mA.cm -2
  • the electrodepositing time is 5 minutes.
  • the source of copper (Cu) may be chosen in the group comprising CuBr 2 , CuCl 2 and CuSO 4 .
  • the source of copper may be an electrolyte comprising CuBr 2 , sodium tartrate dibasic dihydrate and KOH.
  • the electrodeposition of copper may be done using a carbon based-gas diffusion layer (GDL), a Pt plate, and Ag/AgCl (saturated with KCI) respectively as the working, counter, and reference electrodes, respectively.
  • the process can be done using a 2-electrode configuration using a carbon based-gas diffusion layer (GDL) and a Pt plate respectively as the working and counter electrodes, respectively.
  • the copper may be electrodeposited in a raspberry-like morphology.
  • the process according to the invention may further comprise a pre-treatment step a') (prior to step a)) of electrodepositing Ag, Bi, Zn and/or Sn on the porous gas diffusion layer.
  • the source of Ag, Bi, Zn and/or Sn may be chosen in the group comprising -NO 3 , CH 3 COO-, and/or -CI.
  • the source of Ag, Bi, Zn and/or Sn may be an electrolyte comprising AgNO 3 , CH 3 COOAg, Bi(NO 3 ) 3 ⁇ 5H 2 O, ZnCl 2 and/or SnCl 4 , sodium tartrate dibasic dihydrate and KOH.
  • the pre-treatment step a') may be done under the same conditions as step a) in terms of current density, quantity of deposited metal and pulse deposition or galvanostatic method.
  • the step b) of the process according to the invention may be performed in water, organic solvent(s) and mixtures thereof.
  • the organic solvents may be chosen from ethanol, acetonitrile, methanol, acetone, propanol, tetrahydrofuran and mixtures thereof.
  • the concentration of the diazonium salt of formula I in the water and/or an organic solvent may be from 1 to 100 mM, preferably from 2 to 10 mM.
  • the diazonium salt is 4, 2-methyl-4-([2-methylphenyl]azo)benzenediazonium salt, the preferred concentration is 3 mM.
  • the step b) of the process according to the invention may be done under galvanostatic method with a current density from 0.1 to 5 mA.cm -2 , preferably from 0.2 to 2.5 mA.cm -2 , and more preferably at 0.75 mA.cm -2 .
  • the step b) of the process according to the invention may have a duration from 5 seconds to 30 minutes, preferably from 30 seconds to 10 minutes and more preferably 100 seconds.
  • Step b) may be performed at a temperature from 5°C to 80 °C, preferably at room temperature (i.e., from 15 to 30 °C).
  • the process according to the invention may further comprise a step c) of spray coating an ionomer of formula III: wherein, m and n are integers from 1 to 50,000.
  • the process according to the invention may further comprise a step d) of washing the obtained catalyst compound with deionized water.
  • the invention also relates to a catalyst compound obtained by the process according to the invention.
  • the invention relates to a catalyst compound comprising a porous gas diffusion layer, said porous gas diffusion layer being at least partially coated by copper atoms, wherein at least one copper atom is functionalised by a substituent of formula I': wherein Ar A , R A and a are defined as above and represents the point of attachment to copper.
  • the compound according to the invention may be chosen from catalyst compounds comprising a porous gas diffusion layer, said porous support being at least partially coated by copper atoms, wherein at least one copper atom is functionalised by a substituent of one or more of the following formulas: Table 2: example of substituents
  • substituents names Cation ions 2-methyl-4-[(2-methylphenyl)diazenyl]phenyl 4-[(4-methoxyphenyl)amino]phenyl 2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl]phenyl 4-methoxyphenyl 4-Bromophenyl 4-nitrophenyl 4-(diethylamino)phenyl wherein represents the point of attachment to copper.
  • the compound according to the invention may further comprise a Ag, Bi, Zn and/or Sn atom layer in between the porous gas diffusion layer and the copper layer.
  • the copper may be in a raspberry-like morphology, while higher deposition currents will form dendritic fern-like structure.
  • the compound according to the invention may comprise from 70 to 100 at.% of copper atoms, preferably 85 at.%, with regards to the total number of metal atoms in the compound.
  • the compound according to the invention may have an Ar A /Cu atomic surface ratio from 1 to 3, preferably from 1 and 2.
  • the Ar A /Cu atomic surface ratio, in number of atoms, is estimated from the top 5 nm of the surface of the compound and measured by X-ray photoelectron spectroscopy.
  • the compound according to the invention may comprise from 0.5 to 50 at.% of Ag, Bi, Zn and/or Sn atoms, preferably 6 at.%, with regards to the total number of metal atoms in the compound.
  • the compound according to the invention may have an Ar A /(Ag, Bi, Zn and/or Sn) atomic surface ratio from 1 to 3, preferably from 1 and 2.
  • the Ar A /(Ag, Bi, Zn and/or Sn) atomic surface ratio, in number of atoms, is estimated from the top 5 nm of the surface of the compound and measured by X-ray photoelectron spectroscopy.
  • the compound according to the invention may comprise a porous gas diffusion layer, preferably a commercial carbon-based gas diffusion electrode.
  • the structure of the catalyst compound according to the invention is such as the porous gas diffusion layer is coated by a functionalized copper layer and may optionally comprise an in-between layer of Ag, Bi, Zn and/or Sn atom layer in between the porous gas diffusion layer and the copper layer.
  • the invention further relates to the use of the catalyst compound according to the invention as a catalyst, preferably to convert CO 2 into small molecules. It is meant by small molecules, molecules such as gaseous hydrocarbons (methane, ethylene) or liquid molecules (ethanol, formic acid). H 2 may be formed from the electrolysis of water (side-reaction). According to the invention, the conversion of CO 2 mainly leads to C 2 H 4 . Ethylene may represent up to ⁇ 82.4 % (volume ratio) of the gas products (the normalized concentration of CO and ethylene are 5.1 and 24 in GC) of the conversion of CO 2 .
  • the invention further relates to a process of conversion of CO 2 into small molecules comprising a step of contacting CO 2 (gas) with a catalyst compound according to the invention.
  • the conversion reaction of CO 2 may be done under atmospheric pressure and at room temperature (i.e., from 15 to 30°C).
  • the conversion reaction of CO 2 mainly leads to C 2 H 4 .
  • Ethylene may represent up to ⁇ 82.4 % (volume ratio) of the gas products (the normalized concentration of CO and ethylene are 5.081 and 23.959 in GC) of the conversion of CO 2 .
  • the conversion of CO 2 to products is conducted at room temperature and (25°C, 1 atm) with the periodic electrolyte of 0.5 M KHCO 3 .
  • the reactant of CO 2 is continuously flow into the membrane electrode assembly cell with the flow rate of 10 sccm.
  • the electrodeposition of Cu was conducted on a potentiostat. Firstly, to electrodeposit Cu, an electrolyte composed of 0.1 M copper bromide (98%, Sigma-Aldrich), 0.2 M sodium tartrate dibasic dihydrate (purum pro analysis ⁇ 98.0% non-aqueous titration (NT), Sigma-Aldrich), and 1 M KOH was prepared. Acid-treated gas diffusion layer (GDL), Pt plate, and Ag/AgCl (saturated with KCI) were used as the working, counter, and reference electrodes, respectively. The Cu was electrodeposited galvanostatically on the GDL at a constant current density of 15 mA cm -2 . The loading amount of Cu is 4.5 C cm -2 with electrodepositing time of 300 seconds.
  • Cu is successively electrodeposited on the support by controlling the voltage or the current density in order to control the morphology of the deposited.
  • Cu was successively electrodeposited using a current density of 15 mA cm -2 .
  • the loading of Cu is comprised 4.5 C cm -2 .
  • the catalyst compound precursor 1 was obtained.
  • the raspberry structured copper gave the performance in term of Faradaic efficiency (FE) towards C 2 H 4 of 40% at -3.8 V in a MEA electrolyzer (Table 1).
  • Different diazonium salts functional groups of formula I were attached on the catalyst compound precursor 1 by an electroreduction method.
  • the different diazonium salts molecules that have been tested are shown in Figures 2 , 3 and 4 .
  • the functionalization of the catalyst compound precursor 1 was performed in water.
  • the concentration of the diazonium salt of formula I, and reaction conditions are detailed in table 3 below.
  • the electrodes were functionalized using the same optimized conditions in order to compare the performance of the different functional groups and the performances were recorded under the exact same conditions (electrolyte, temperature, time).
  • the obtained electrodes (catalyst compounds 1A-1G) were washed with water and dried with Ar.
  • the catalyst compounds 1A-1G were obtained.
  • Table 3 reaction conditions C. No Reagents / concentration / solvent Cation ions Anion ions 1A 4, 2-Methyl-4-([2-methylphenyl] azo) benzenediazonium salt 3 mM in water 1B 4-Amino-4'-methoxydiphenylamine-diazonium chloride 3 mM in water Cl - 1C dichlorozinc;2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl] benzenediazonium; dichloride 3 mM in water Cl - .
  • the catalysts according to the invention prepared and tested in the example allowed improving the performance towards the production of C 2 H 4 molecule at room temperature and atmospheric pressure. Compared to traditional Cu electrocatalyst, the Faradaic efficiency towards ethylene are increased by 43% and 49% for 1A and 1I groups modified Cu.
  • the new electrocatalysts according to the invention are more energy efficient.

Abstract

The present invention belongs to the field of catalytic chemistry, and more specifically to catalysed reduction chemical reactions, preferably of CO2 into small molecules.
The present invention relates to a new catalyst compound comprising at least a copper (Cu) layer, wherein the copper layer is functionalized with at least one aryl group and its use thereof in a reduction chemical reaction, preferably in reduction of CO2 into CO, ethylene and other small molecules such as gaseous hydrocarbons (methane, propane) or liquid molecules (ethanol, formic acid, propanol). The invention relates to the process of manufacture of said catalyst compound and to a process electrochemical conversion of CO2 to small molecules and in particular ethylene.

Description

    Technical field
  • The present invention belongs to the field of catalytic chemistry, and more specifically to catalysed reduction chemical reactions, preferably of CO2 into small molecules.
  • The present invention relates to a new catalyst compound comprising at least a copper (Cu) layer, wherein the copper layer is functionalized with at least one aryl functional group and its use thereof in a reduction chemical reaction, preferably in reduction of CO2 into CO, ethylene and other small molecules such as gaseous hydrocarbons (methane, propane) or liquid molecules (ethanol, formic acid, propanol). The invention relates to the process of manufacture of said catalyst compound and to a process electrochemical conversion of CO2 to small molecules and in particular ethylene.
  • In the description below, references between [1-4] refer to the list of references at the end of the examples.
    • Technical background
  • The release of carbon dioxide (CO2) is a major concern for the environment. Its capture and recycling into small organic bricks such as carbon monoxide (CO), formic acid (HCOOH), methane (CH4) or methanol (CH3OH), ethanol (C2H5OH) and ethylene (C2H4) could prove to be very advantageous.
  • Particularly, the electrochemical conversion of CO2 into small molecules such as gaseous hydrocarbons (methane, ethylene) or liquid molecules (ethanol, formic acid) is an attractive method as these molecules can be used as fuels or organic bricks to produce longer hydrocarbon molecules [1-3]. Currently only copper-based catalysts (Cu) can convert CO2 in small organic molecules, but their efficiency is still limited - preventing its use in industrial process [4].
  • Therefore, there is a critical necessity to explore for an easier and cheaper way to produce small molecules such as ethylene and gaseous hydrocarbons (methane, ethylene) or liquid molecules (ethanol, formic acid) from CO2 in a cheap and environmentally friendly procedure.
    • Detailed description of the invention
  • Applicant has developed a new process and a new catalyst compound that solves all of the problems listed above.
  • The present invention deals with a new process and a new catalyst compound, and its applications, such as a method to convert CO2 into small molecules, more preferably ethylene, at room temperature and atmospheric pressure. Being able to produce such small molecules at room temperature and atmospheric pressure in large quantities is, to the knowledge of Applicant, something that was not observed in the art.
  • Applicant surprisingly found out that using a functionalized Cu catalyst made according to process of the invention gives very good yields in conversion of CO2 into small molecules such as ethylene and gaseous hydrocarbons (methane, ethylene) or liquid molecules (ethanol, formic acid). Specifically, it was identified that the performance is considerably improved by grafting specific functional groups on the surface of inorganic electrocatalysts. These functional groups, substituted aryl groups, allow increasing the current density and improving the Faradaic efficiency of the reaction towards the production of ethylene up to about 83% at -3.55 V in a membrane-electrode-assembly cell (MEA).
  • The catalyst compound of the invention is based on copper (Cu) and optionally Ag, Bi, Zn and/or Sn crystal grown on a porous gas diffusion layer (typically a commercial carbon support such as a gas diffusion electrode or a porous polymer substrate such as PTFE, nylon or PVDF) via electrodeposition and then functionalization with various substituted aryl groups. The catalyst compound obtained by the process of the invention may present a raspberry-like morphology.
  • A first object of the invention is a process of manufacture of a catalyst compound comprising the steps of:
    1. a) electrodepositing copper on a porous gas diffusion layer, the porous gas diffusion layer being optionally pre-treated;
    2. b) functionalisation of the metal catalyst obtained in step a) by contacting with a diazonium salt of formula I:
      Figure imgb0001
       wherein,
      • X- represents an anion,
      • a is an integer from 1 to 3,
      • ArA represents an aryl group, substituted by at least one -RA group,
      • -RA represents at least one substituent chosen from a halo group, - R1, -NO2, -OR1, -NR2R3 and a group of formula II:
        Figure imgb0002
         in which,
        • ∘ -R1 represents a C1 to C3 alkyl group,
        • ∘ -R2 and R3 independently represent H or a C1 to C3 alkyl group,
        • ∘ b is an integer from 1 to 3,
        • ∘ FB is a functional group chosen from -N=N- and -NH-,
        • ∘ ArB represents an aryl group, substituted by at least one -RB group,
        • ∘ -RB represents at least one substituent chosen from a halo group, -R1, -OR1 and -NR2R3,
        • Figure imgb0003
           represent the point of attachment to ArA.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein X- is chosen from BF4 -, Cl- and HSO4 -.
  • It is meant by "aryl", a group derived from arenes by removal of a hydrogen atom from a ring carbon atom; arenes being monoyclic and polycyclic aromatic hydrocarbons (IUPAC). According to the invention aryl groups may comprise from 4 to 10 carbon atoms, preferably 6 carbon atoms. According to the invention, aryl groups ArA and ArB do not comprise, heteroatoms besides the heteroatoms comprised in RA, FB and RB.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein ArA and/or ArB are aryl groups comprising 6 carbon atoms and are phenyl groups. Preferably, ArA and/or ArB are phenyl groups substituted by at least one -RA group in ortho, meta and/or para position.
  • Advantageously, when ArA is substituted by more than one RA group (i.e, a = 2 or 3), the RA groups may be identical or different from each other.
  • Advantageously, when ArB is substituted by more than one RB group (i.e, b = 2 or 3), the RB groups may be identical or different from each other.
  • In other terms, when there is more than one RA substituent, the RA substituents may be identical or different from each other and/or when there is more than one RB substituent, the RB substituents may be identical or different from each other. Also, when there is RA and RB groups, the RA and RB groups may be identical or different. For example, when there are two RA, they may both be R1, and yet be identical or different (e.g. one may be -Me and the other may be -Et or they may both be -Me). Also, for example, when one RA substituent and one RB substituent are both R1, they may be identical or different (e.g. one may be -Me and the other may be -Et or they may both be -Me).
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein a = 1 or 2.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein b = 1 or 2, more preferably 1.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RA is a halo group, preferably chosen from Br, Cl and I.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RA is -NO2.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RA is -R1, preferably chosen from - Me, -Et and -Pr (Pr being either isopropyl or n-propyl).
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RA is -OR1, preferably chosen from - OMe, -OEt and -OPr (Pr being either isopropyl or n-propyl).
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RA is -NR2R3, preferably chosen from -NEt2, -NMe2, -NPr2, -NMeEt and -NMePr (Pr being either isopropyl or n-propyl). Advantageously, the diazonium salt may be chosen from diazonium salt of formula I, wherein at least one RA group is a group of formula II.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RB is a halo group, preferably chosen from Br, Cl and I.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RB is -NO2.
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RB is -R1, preferably chosen from - Me, -Et and -Pr (Pr being either isopropyl or n-propyl).
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RB is -OR1, preferably chosen from - OMe, -OEt and -OPr (Pr being either isopropyl or n-propyl).
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RB is -NR2R3, preferably chosen from -NEt2, -NMe2, -NPr2, -NMeEt and -NMePr (Pr being either isopropyl or n-propyl).
  • Advantageously, the diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RA group is a group of formula II and ArA and ArB are each substituted by one -R1 group, preferably -Me. The diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RA group is a group of formula II and ArA is substituted by two - OR1 groups, preferably -OMe and ArB is substituted by one -NO2 group. The diazonium salt may be chosen from diazonium salts of formula I, wherein at least one RA group is a group of formula II and ArB is substituted by one - OR1 group, preferably -OMe.
  • Advantageously, the diazonium salt may be chosen from the following salts: Table 1: example of salts
    Salts names (IUPAC) Diazonium X-
    2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazoniu m
    Figure imgb0004
    Figure imgb0005
    4-[(4-methoxyphenyl)amino]benzene-1-diazonium chloride
    Figure imgb0006
         		Cl-
    dichlorozinc;2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl]benzenediazonium; dichloride
    Figure imgb0007
         		Cl-. ½ ZnCl2
    4-methoxybenzenediazonium;tetrafluorobo rate
    Figure imgb0008
         		BF4 -
    4-B romobenzenediazonium;tetrafluorobora te
    Figure imgb0009
         		BF4 -
    4-nitrobenzenediazonium; tetrafluoroborate
    Figure imgb0010
         		BF4 -
    4-(diethylamino)benzenediazonium;tetraflu oroborate
    Figure imgb0011
         		BF4 -
  • The different anions in the table above may be used independently to the nature of the cations. For example, "2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium", "4-[(4-methoxyphenyl)amino]benzene-1-diazonium chloride" or "dichlorozinc;2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl]benzenediazonium;dichloride" may have BF4 - as counter anion.
  • Advantageously, the diazonium salt of formula I may be chosen from the following salts:
    Figure imgb0012
    Figure imgb0013
  • Advantageously, step a) and/or step b) of the process according to the invention may be conducted using a potentiostat.
  • Advantageously, the porous gas diffusion layer may be a commercial conducting carbon-based gas diffusion electrode or a porous polymer substrate such as (PTFE, nylon, PVDF).
  • Advantageously, step a) and/or step b) of the process according to the invention may be conducted under a current density from 5 mA.cm-2 to 50 mA.cm-2, preferably from 10 mA.cm-2 to 20 mA.cm-2 , and more preferably at 15 mA.cm-2.
  • Advantageously, in step a) of the process according to the invention, the quantity of deposited Cu may be from 0.5 C.cm-2 to 50 C.cm-2, preferably between 15 C.cm-2 to 35 C.cm-2, more preferably at 15 mA.cm-2.
  • Advantageously, step a) and/or step b) of the process according to the invention may be done under pulse deposition or galvanostatic method. Preferably, the applied current density for electrodepositing copper is 15 mA.cm-2 , and the electrodepositing time is 5 minutes.
  • Advantageously, in the step a) of the process according to the invention, the source of copper (Cu) may be chosen in the group comprising CuBr2, CuCl2 and CuSO4. The source of copper may be an electrolyte comprising CuBr2, sodium tartrate dibasic dihydrate and KOH.
  • Advantageously, in the step a) of the process according to the invention, the electrodeposition of copper may be done using a carbon based-gas diffusion layer (GDL), a Pt plate, and Ag/AgCl (saturated with KCI) respectively as the working, counter, and reference electrodes, respectively. Alternatively, the process can be done using a 2-electrode configuration using a carbon based-gas diffusion layer (GDL) and a Pt plate respectively as the working and counter electrodes, respectively.
  • Advantageously, in step a) of the process according to the invention, the copper may be electrodeposited in a raspberry-like morphology.
  • Advantageously, the process according to the invention may further comprise a pre-treatment step a') (prior to step a)) of electrodepositing Ag, Bi, Zn and/or Sn on the porous gas diffusion layer. In the pre-treatment step a') of the process according to the invention, the source of Ag, Bi, Zn and/or Sn may be chosen in the group comprising -NO3, CH3COO-, and/or -CI. The source of Ag, Bi, Zn and/or Sn may be an electrolyte comprising AgNO3, CH3COOAg, Bi(NO3)3·5H2O, ZnCl2 and/or SnCl4, sodium tartrate dibasic dihydrate and KOH. The pre-treatment step a') may be done under the same conditions as step a) in terms of current density, quantity of deposited metal and pulse deposition or galvanostatic method.
  • Advantageously, the step b) of the process according to the invention may be performed in water, organic solvent(s) and mixtures thereof. The organic solvents may be chosen from ethanol, acetonitrile, methanol, acetone, propanol, tetrahydrofuran and mixtures thereof. The concentration of the diazonium salt of formula I in the water and/or an organic solvent may be from 1 to 100 mM, preferably from 2 to 10 mM. For example, when the diazonium salt is 4, 2-methyl-4-([2-methylphenyl]azo)benzenediazonium salt, the preferred concentration is 3 mM.
  • Advantageously, the step b) of the process according to the invention may be done under galvanostatic method with a current density from 0.1 to 5 mA.cm-2, preferably from 0.2 to 2.5 mA.cm-2 , and more preferably at 0.75 mA.cm-2.
  • Advantageously, the step b) of the process according to the invention may have a duration from 5 seconds to 30 minutes, preferably from 30 seconds to 10 minutes and more preferably 100 seconds. Step b) may be performed at a temperature from 5°C to 80 °C, preferably at room temperature (i.e., from 15 to 30 °C).
  • Advantageously, the process according to the invention may further comprise a step c) of spray coating an ionomer of formula III:
    Figure imgb0014
     wherein,
    m and n are integers from 1 to 50,000.
  • Advantageously, the process according to the invention may further comprise a step d) of washing the obtained catalyst compound with deionized water.
  • The invention also relates to a catalyst compound obtained by the process according to the invention.
  • The invention relates to a catalyst compound comprising a porous gas diffusion layer, said porous gas diffusion layer being at least partially coated by copper atoms, wherein at least one copper atom is functionalised by a substituent of formula I':
    Figure imgb0015
     wherein ArA, RA and a are defined as above and
    Figure imgb0016
    represents the point of attachment to copper.
  • Advantageously, the compound according to the invention may be chosen from catalyst compounds comprising a porous gas diffusion layer, said porous support being at least partially coated by copper atoms, wherein at least one copper atom is functionalised by a substituent of one or more of the following formulas: Table 2: example of substituents
    Substituents names Cation ions
    2-methyl-4-[(2-methylphenyl)diazenyl]phenyl
    Figure imgb0017
    4-[(4-methoxyphenyl)amino]phenyl
    Figure imgb0018
    2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl]phenyl
    Figure imgb0019
    4-methoxyphenyl
    Figure imgb0020
    4-Bromophenyl
    Figure imgb0021
    4-nitrophenyl
    Figure imgb0022
    4-(diethylamino)phenyl
    Figure imgb0023
    wherein
    Figure imgb0024
    represents the point of attachment to copper.
  • Advantageously, the compound according to the invention may further comprise a Ag, Bi, Zn and/or Sn atom layer in between the porous gas diffusion layer and the copper layer.
  • Advantageously, in the compound according to the invention, the copper may be in a raspberry-like morphology, while higher deposition currents will form dendritic fern-like structure.
  • Advantageously, the compound according to the invention, may comprise from 70 to 100 at.% of copper atoms, preferably 85 at.%, with regards to the total number of metal atoms in the compound.
  • Advantageously, the compound according to the invention, may have an ArA/Cu atomic surface ratio from 1 to 3, preferably from 1 and 2. The ArA/Cu atomic surface ratio, in number of atoms, is estimated from the top 5 nm of the surface of the compound and measured by X-ray photoelectron spectroscopy.
  • Advantageously, the compound according to the invention, may comprise from 0.5 to 50 at.% of Ag, Bi, Zn and/or Sn atoms, preferably 6 at.%, with regards to the total number of metal atoms in the compound.
  • Advantageously, the compound according to the invention, may have an ArA/(Ag, Bi, Zn and/or Sn) atomic surface ratio from 1 to 3, preferably from 1 and 2. The ArA/(Ag, Bi, Zn and/or Sn) atomic surface ratio, in number of atoms, is estimated from the top 5 nm of the surface of the compound and measured by X-ray photoelectron spectroscopy.
  • Advantageously, the compound according to the invention, may comprise a porous gas diffusion layer, preferably a commercial carbon-based gas diffusion electrode. The structure of the catalyst compound according to the invention is such as the porous gas diffusion layer is coated by a functionalized copper layer and may optionally comprise an in-between layer of Ag, Bi, Zn and/or Sn atom layer in between the porous gas diffusion layer and the copper layer.
  • Some advantages of the catalyst compound according to the invention are listed below:
    • the catalyst compound according to the invention has an increased current density and an improved selectivity of the reaction towards the production of C2 molecules (mainly ethylene) up to -213 mA.cm-2 and a Faradaic efficiency > 80 % at a full cell potential (Vcathode-Vanode) of -3.55 V compared to -122 mA.cm-2 and ~40 % for pristine non-functionalized Cu-based electrocatalyst at -3.80 V when measured in a 2-electrode configuration;
    • the catalyst compound according to the invention can be easily obtained by electrodepositing Cu and optionally Ag, Bi, Zn and/or Sn metals in the form of a flower structure for larger active surface;
    • the functionalization step b) is easy and cheap as the molecules needed are very common and easily obtainable;
    • the catalyst compound according to the invention allows the production of high concentrated gaseous product, notably C2 products and more specifically ethylene molecule with high added values
    • the catalyst compound according to the invention have a total current density over 683 mA m-2 at -3.9 V in a 2-electrode configuration;
    • the catalyst compound according to the invention have a specific current density over 536 mA m-2 for ethylene for CO2RR at -3.9 V, which means 461 g m-2h-1 of ethylene.
  • The invention further relates to the use of the catalyst compound according to the invention as a catalyst, preferably to convert CO2 into small molecules. It is meant by small molecules, molecules such as gaseous hydrocarbons (methane, ethylene) or liquid molecules (ethanol, formic acid). H2 may be formed from the electrolysis of water (side-reaction). According to the invention, the conversion of CO2 mainly leads to C2H4. Ethylene may represent up to ~82.4 % (volume ratio) of the gas products (the normalized concentration of CO and ethylene are 5.1 and 24 in GC) of the conversion of CO2.
  • The invention further relates to a process of conversion of CO2 into small molecules comprising a step of contacting CO2 (gas) with a catalyst compound according to the invention. The conversion reaction of CO2 may be done under atmospheric pressure and at room temperature (i.e., from 15 to 30°C). According to invention, the conversion reaction of CO2 mainly leads to C2H4. Ethylene may represent up to ~82.4 % (volume ratio) of the gas products (the normalized concentration of CO and ethylene are 5.081 and 23.959 in GC) of the conversion of CO2.
  • The conversion of CO2 to products (mainly gas products, CO and ethylene) is conducted at room temperature and (25°C, 1 atm) with the periodic electrolyte of 0.5 M KHCO3. The reactant of CO2 is continuously flow into the membrane electrode assembly cell with the flow rate of 10 sccm.
    • Brief description of the figures
    • Figure 1. Low-magnification scanning electron microscopy (SEM) images for the pristine and functionalized Cu catalysts. (a) Precursor 1 (Cu), (b1) 1A and (b2) the cross-section of 1A.
    • Figure 2. Comparison of FEs for ethylene on different Cu electrodes measured at full-cell potentials ranging from -3.0 to -4.0 V and measured in 0.5 M KHCO3. Cu refers to Precursor 1, unfunctionalized Cu catalyst; 1A, 1B, 1C, 1D, 1E, 1F and 1G respectively refer to Cu modified with 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium; 4-[(4-methoxyphenyl)amino]benzene-1-diazonium chloride; dichlorozinc;2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl]benzenediazonium; dichloride; 4-methoxybenzenediazonium;tetrafluoroborate; 4-Bromobenzenediazonium;tetrafluoroborate; 4-nitrobenzenediazonium;tetrafluoroborate and 4-(diethylamino)benzenediazonium;tetrafluoroborate; and 1I refers to Cu modified with 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium and the ionomer.
    • Figure 3. The total current density from different functionalized electrodes in membrane-electrode-assembly reactor (MEA). Cu refers to Precursor 1, unfunctionalized Cu catalyst; 1A, 1B, 1C, 1D, 1E, 1F and 1G respectively refer to Cu modified with 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium; 4-[(4-methoxyphenyl)amino]benzene-1-diazonium chloride; dichlorozinc;2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl]benzenediazonium; dichloride; 4-methoxybenzenediazonium;tetrafluoroborate; 4-Bromobenzenediazonium;tetrafluoroborate; 4-nitrobenzenediazonium;tetrafluoroborate and 4-(diethylamino)benzenediazonium;tetrafluoroborate; and 1I refers to Cu modified with 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium and the ionomer.
    • Figure 4. The C2H4 specific current density from different functionalized electrodes in membrane-electrode-assembly reactor (MEA). Cu refers to Precursor 1, unfunctionalized Cu catalyst; 1A, 1B, 1C, 1D, 1E, 1F and 1G respectively refer to Cu modified with 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium; 4-[(4-methoxyphenyl)amino]benzene-1-diazonium chloride; dichlorozinc;2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl]benzenediazonium; dichloride; 4-methoxybenzenediazonium;tetrafluoroborate; 4-Bromobenzenediazonium;tetrafluoroborate; 4-nitrobenzenediazonium;tetrafluoroborate and 4-(diethylamino)benzenediazonium;tetrafluoroborate; and 1I refers to Cu modified with 2-methyl-4-[(2-methylphenyl)diazenyl]benzenediazonium and the ionomer.
    EXAMPLES Example 1: Preparation of a catalyst compound precursor 1
  • The electrodeposition of Cu was conducted on a potentiostat. Firstly, to electrodeposit Cu, an electrolyte composed of 0.1 M copper bromide (98%, Sigma-Aldrich), 0.2 M sodium tartrate dibasic dihydrate (purum pro analysis ≥ 98.0% non-aqueous titration (NT), Sigma-Aldrich), and 1 M KOH was prepared. Acid-treated gas diffusion layer (GDL), Pt plate, and Ag/AgCl (saturated with KCI) were used as the working, counter, and reference electrodes, respectively. The Cu was electrodeposited galvanostatically on the GDL at a constant current density of 15 mA cm-2. The loading amount of Cu is 4.5 C cm-2 with electrodepositing time of 300 seconds.
  • Firstly, Cu is successively electrodeposited on the support by controlling the voltage or the current density in order to control the morphology of the deposited. Cu was successively electrodeposited using a current density of 15 mA cm-2. The loading of Cu is comprised 4.5 C cm-2.
  • The best performance is obtained when the copper is grown in the form of a raspberry structure using a galvanostatic deposition method where the applied current density is 15 mA cm-2 (Figure. 1). The source of Cu used for the electrodeposition at CuBr2 (CAS: 7789-45-9).
  • The catalyst compound precursor 1 was obtained.
    • Example 2: Synthesis of the catalyst compounds 1A-1G according to the invention
  • The raspberry structured copper gave the performance in term of Faradaic efficiency (FE) towards C2H4 of 40% at -3.8 V in a MEA electrolyzer (Table 1).
  • Different diazonium salts functional groups of formula I were attached on the catalyst compound precursor 1 by an electroreduction method. The different diazonium salts molecules that have been tested are shown in Figures 2, 3 and 4. The functionalization of the catalyst compound precursor 1 was performed in water. The concentration of the diazonium salt of formula I, and reaction conditions are detailed in table 3 below. The electrodes were functionalized using the same optimized conditions in order to compare the performance of the different functional groups and the performances were recorded under the exact same conditions (electrolyte, temperature, time). The obtained electrodes (catalyst compounds 1A-1G) were washed with water and dried with Ar.
  • The catalyst compounds 1A-1G were obtained. Table 3: reaction conditions
    C. No Reagents / concentration / solvent Cation ions Anion ions
    1A 4, 2-Methyl-4-([2-methylphenyl] azo) benzenediazonium salt 3 mM in water
    Figure imgb0025
    Figure imgb0026
    1B 4-Amino-4'-methoxydiphenylamine-diazonium chloride 3 mM in water
    Figure imgb0027
         		Cl -
    1C dichlorozinc;2,5-dimethoxy-4-[(4-nitrophenyl)diazenyl] benzenediazonium; dichloride 3 mM in water
    Figure imgb0028
         		Cl-. ½ ZnCl 2
    1D 4-Methoxybenzenediazonium tetrafluoroborate 3 mM in water
    Figure imgb0029
         		BF 4 -
    1E 4-Bromobenzenediazonium tetrafluoroborate 3 mM in water
    Figure imgb0030
         		BF4 -
    IF 4-Nitrobenzenediazonium tetrafluoroborate 3 mM in water
    Figure imgb0031
         		BF 4 -
    1G 4-Diazo-N,N-Diethylaniline fluoroborate 3 mM in water
    Figure imgb0032
         		BF4 -
    • Example 3: Performances of the catalyst compounds 1A-1G according to the invention
  • The catalytic performance of compounds 1A to 1G is presented in table 4 below: Table 4: Summary of the electrocatalytic performance for pristine and functionalized Cu electrodes.
    Electrode Cell voltages (V) Faradaic efficiency (FE, %)
    Precursor 1 (Cu) H2 CO HCOOH C2H4 C2H5OH
    -3.0 64.2±1.0 31.9±1.0 0 4.1±0.9 0
    -3.2 57.4±2.3 29.8±0.9 0 11.4±2.7 0
    -3.4 47.9±2.5 27.9±0.7 1.8±0.6 19.4±1.7 0
    -3.5 41.7±0.9 26.6±0.8 2.2±0.6 26.5±1.6 1.8±0.5
    -3.55 40.8±1.6 25.3±0.9 2.8±0.6 28.0±1.3 3.6±1.1
    -3.6 37.1±1.2 24.3±1.2 3.2±0.7 29.8±1.4 4.2±0.9
    -3.65 36.9±1.9 22.2±1.4 5.1±0.6 31.9±2.3 5.7±1.1
    -3.7 35.9±1.5 21.7±0.7 4.5±0.8 35.3±2.3 7.1±2.0
    -3.75 32.8±0.4 19.6±0.7 3.2±0.8 38.4±1.5 8.1±2.1
    -3.8 32.8±0.4 18.4±0.5 2.1±0.7 40.2±1.4 11.9±3.0
    -3.85 37.9±0.8 17.5±0.5 1.4±0.5 38.6±0.8 10.6±1.0
    -3.9 43.9±1.1 16.4±0.6 1.5±0.5 36.2±0.4 8.7±2.0
    -4.0 48.5±1.7 14.1±1.0 1.0±0.6 32.7±0.4 4.9±0.357.7
    1G -3.0 47.3±1.1 12.3±0.8 0 32.0±5.9 0
    -3.2 42.9±1.3 10.6±1.1 0 43.2±1.6 0
    -3.4 38.1±1.2 8.7±1.1 0.9±0.2 52.7±2.6 0.6±0
    -3.5 32.1±0.2 9.1±1.2 1.0±0.5 57.9±2.9 0.6±0.3
    -3.55 28.4±0.7 7.9+1.5 1.2±0.5 63.0±2.7 0.9±0.5
    -3.6 24.6±0.9 6.2±1.3 1.4±0.4 67.8±3.1 1.4±0.3
    -3.65 21.7±1.2 5.3±0.5 1.5±0.8 72.9±2.9 1.9±0.5
    -3.7 23.7±0.7 4.6±0.6 1.1±0.4 68.3±3.1 2.3±1.1
    -3.75 26.6±0.5 4.1±0.6 0.7±0.5 65.4±2.3 3.2±1.3
    -3.8 37.6±1.0 3.3±0.6 0.7±0.4 57.9±1.7 2.5±1.4
    -3.85 47.9±0.8 2.2±0.5 0.6±0.4 49.3±2.7 2.0±0.8
    -3.9 53.3±0.8 1.8±0.5 0.6±0.4 42.7±1.5 1.6±0.4
    -4.0 57.7±0.6 1.8±0.1 0.5±0.2 39.0±0.8 1.5±0.7
    1D -3.0 33.0±7.7 22.8±1.1 0 40.2±3.1 0
    -3.2 26.2±2.1 24.3±1.9 0 48.9±4.3 0
    -3.4 23.6±2.7 20.1±2.1 0.9±0.3 53.6±5.6 1.0±1.9
    -3.5 23.2±3.4 15.4±1.7 0.9±0.8 57.3±3.2 1.5±2.7
    -3.55 18.7±2.9 10.3±1.6 1.3±0.6 65.4±3.7 2.9±4.2
    -3.6 16.4±3.2 9.0±4.7 1.4±0.8 72.2±5.3 3.1±3.3
    -3.65 15.3±3.4 6.7±1.6 1.5±0.8 78.0±2.7 3.8±4.5
    -3.7 14.3±3.5 5.3±2.3 1.3±0.8 76.4±4.1 5.1±4.6
    -3.75 16.9±4.2 3.6±1.0 1.2±0.7 74.3±2.7 3.8±3.0
    -3.8 19.5±5.4 3.2±1.9 1.4±0.6 71.1±4.9 3.3±3.1
    -3.85 22.8±7.1 2.7±1.9 0.8±0.7 70.6±2.2 2.3±3.1
    -3.9 24.1±8.4 2.4±0.8 1.1±0.8 70.0±3.3 1.9±2.9
    -4.0 29.3±0.9 2.5±0.3 0.8±0.2 65.6±0.6 1.2±0.4
    1B -3.0 47.3±2.5 35.4±3.0 0 15.5±2.0 0
    -3.2 37.2±2.5 34.1+1.7 0.3±0.1 22.5±1.7 0
    -3.4 25.9±1.4 31.8±1.4 0.4±0.1 36.6±1.4 1.1±0.1
    -3.5 22.0±1.0 24.6±0.5 0.5±0.1 43.7±0.6 1.3±0.4
    -3.55 20.8±1.3 19.5±1.4 0.7±0.2 51.7±0.9 1.3±0.6
    -3.6 19.1±1.2 14.2±0.1 1.1±0.7 61.7±2.3 2.3±0.8
    -3.65 17.8±1.0 11.0±1.1 1.2±0.8 68.6±2.5 2.5±0.7
    -3.7 16.3±0.6 9.3±0.4 1.2±0.4 72.7±2.0 2.6±1.0
    -3.75 15.3±0.4 7.1±0.7 1.8±0.8 76.8±1.1 2.7±1.1
    -3.8 14.2±0.2 5.5±0.8 1.2±0.8 79.9+0.5 3.3±0.6
    -3.85 15.5±0.4 5.1±0.9 0.9±0.9 78.1±1.7 3.1±1.1
    -3.9 16.5±1.0 4.7±1.2 0.8±0.8 75.3±1.3 3.1±1.2
    -4.0 20.7±0.5 3.4±0.9 0.5±0.6 72.0±0.9 2.3±0.8
    1A -3.0 34.0±2.1 8.0±1.6 0 50.6±1.2 0
    -3.2 25.2±1.4 9.5±1.8 0.2±1.4 62.2±2.5 1.9±1.1
    -3.4 15.4±0.5 10.0±0.4 0.2±1.1 70.3±1.9 2.3±1.0
    -3.5 10.0±1.2 8.5±2.2 2.5±0.8 77.5±2.1 2.3±2.0
    -3.55 8.3±2.8 6.3±1.1 2.3±0.9 83.2±2.4 2.5±1.0
    -3.6 12.3±2.3 5.6±3.0 1.4±0.8 80.0±0.8 2.5±2.0
    -3.65 15.8±3.1 5.4±2.0 1.2±1.0 76.6±0.6 2.6±1.0
    -3.7 19.2±1.2 4.9±2.0 1.3±0.9 71.1±1.8 4.0±1.0
    -3.75 22.1±3.2 4.8±1.1 1.3±1.1 64.1±2.4 4.5±0.8
    -3.8 26.4±4.1 4.4±2.0 1.1±0.9 60.2±1.3 4.4±0.9
    -3.85 30.2±3.3 4.4±3.1 0.9±1.1 55.9±1.6 4.8±1.0
    -3.9 34.8±2.4 4.0±1.2 0.8±1.0 53.0±2.4 3.9±1.1
    -4.0 38.4±3.1 3.9±0.9 0.7±1.3 52.3±1.1 3.6±0.8
    1C -3.0 54.3±1.1 4.4±0.9 0 32.1±6.0 0
    -3.2 49.5±1.3 4.4±1.1 0 38.9±1.7 0
    -3.4 42.8±1.2 5.2±1.1 1.1±0.4 45.1±2.6 1.4±0.4
    -3.5 38.4±0.2 6.1±1.2 2.1±0.2 49.9±2.9 1.3±0.8
    -3.55 34.9±0.7 6.4±1.5 2.6±0.2 53.9±2.7 1.4±0.7
    -3.6 32.3±0.9 7.3±1.3 3.5±0.3 57.9±3.1 1.7±0.8
    -3.65 26.7±1.2 6.3±0.5 3.8±1.0 61.5±2.9 2.4±0.8
    -3.7 23.4±0.7 5.8±0.6 3.2±0.9 66.6±3.1 3.8±0.9
    -3.75 19.5±0.5 4.9±0.6 3.3±0.3 70.4±2.3 4.6±1.2
    -3.8 16.2±1.0 4.2±0.6 2.3±0.4 75.1±1.7 5.1±1.2
    -3.85 19.2±0.8 3.7±0.5 1.2±0.5 71.2±2.7 4.9±1.3
    -3.9 23.3±0.8 3.4±0.5 1.5±0.4 68.2±1.5 3.8±1.1
    -4.0 27.2±2.0 2.5±1.0 1.1±1.0 61.3±2.9 2.7±1.5
    1E -3.0 48.5±3.7 25.0±0.5 0 21.9±0.5 0
    -3.2 43.9±4.7 27.7±1.0 0 25.9±1.0 0
    -3.4 38.2±7 .5 23.1±2.5 0.7±0.9 36.3±1.7 0.7±0.4
    -3.5 34.2±5.3 20.6±3.2 1.5±0.9 42.5±2.2 2.0±0.7
    -3.55 31.5±4.2 15.9±4.0 2.4±1.2 47.0±2.8 2.9±1.2
    -3.6 29.2±2.0 13.4±5.1 3.4±1.1 51.1±3.9 3.5±1.3
    -3.65 26.7±6.4 9.7+6.3 2.3±0.9 57.0±2.1 5.1±1.5
    -3.7 25.8±5.4 7.0±2.9 1.9±0.7 61.7±1.6 6.0±2.6
    -3.75 34.7±5.3 5.9±5.3 1.5±0.6 55.1±4.9 5.5±2.0
    -3.8 42.0±4.1 4.2±2.9 1.2±0.9 48.5±5.9 5.2±2.2
    -3.85 48.9±3.1 2.9±7.9 1.1±0.8 44.5±5.4 4.1±1.1
    -3.9 50.5±3.1 2.6±5.2 0.9±0.7 41.7±5.5 3.1±2.1
    -4.0 56.6±2.1 2.6±3.5 0.8±1.0 37.1±2.8 2.8±1.9
    1F -3.0 48.9±1.2 9.8+1.1 0 35.9±0.9 0
    -3.2 47.3±1.3 12.5±0.4 0 37.2±1.1 0
    -3.4 44.6±1.2 12.6±0.6 0.7±0.3 39.3±1.1 0
    -3.5 43.2±0.8 14.4±0.3 1.2±0.2 43.4±0.8 0.8±0.5
    -3.55 37.4±0.5 10.9±0.6 1.7±0.2 45.9±0.6 1.4±0.4
    -3.6 34.7±0.5 9.7+0.5 1.9±0.0 49.2±0.7 1.9±0.4
    -3.65 33.5±0.3 8.9+0.1 2.9±0.4 51.6±0.5 3.2±0.5
    -3.7 33.5±0.4 7.8±0.1 3.5±0.4 53.5±0.6 4.6±0.4
    -3.75 28.6±0.2 7.0±0.5 2.3±0.3 56.3±0.4 5.6±0.4
    -3.8 32.3±0.4 6.0±0.1 1.1±0.2 57.9±0.8 6.8±0.3
    -3.85 38.9±0.9 5.9±0.2 1.1±0.6 56.3±1.2 4.8±0.3
    -3.9 40.7±0.7 5.4±0.1 1.3±0.1 53.6±0.9 3.7±0.3
    -4.0 45.7±1.3 4.2±0.3 0.7±1.1 49.2±1.4 2.0±1.5
    1I -3.0 66.9±3.5 4.6±0.2 0 23.7±1.0 0
    -3.2 58.9±1.5 5.1±0.3 0 25.3±0.6 0
    -3.4 53.7±1.8 7.1±0.2 1.0±0.5 37.4±1.1 0.6±0.4
    -3.5 47.9±1.1 7.1±0.3 1.4±0.5 43.9±1.8 1.0±0.5
    -3.55 44.9±1.5 5.3±0.1 1.5±0.5 49.4±0.8 1.0±1.1
    -3.6 40.4±1.0 4.8±0.1 1.7±0.4 56.1+1.3 1.2±0.6
    -3.65 34.1±0.9 4.7±0.2 2.0±0.5 64.2±1.8 1.7±1.0
    -3.7 28.9±0.6 4.2±0.1 1.5±0.4 73.6±2.0 2.1±0.5
    -3.75 24.4±0.5 4.2±0.1 1.1±0.5 75.5±1.7 2.5±1.1
    -3.8 17.8±0.1 3.6±0.3 1.1±0.4 86.3±0.5 2.8±1.5
    -3.85 10.2±0.3 4.0±0.1 1.1±0.6 89.7+0.9 2.3±1.0
    -3.9 27.6±0.4 3.2±0.4 1.1±0.4 79.5±1.0 2.3±0.9
    -4.0 33.2±2.2 3.6±1.3 0.6±0.9 73.8±2.1 1.7±1.5
  • The results shown in table 4 demonstrate that both the current density and the Faradaic efficiency are both strongly improved after functionalization. Compounds 1A and 1I groups gave the best results and the Faradaic efficiency towards the formation of C2H4 can reach 83% at - 3.55 V and 89% at -3.9 V compared to 40% for Precursor 1 (Fig. 2). By taking into account the current density, the results show that the specific current density for ethylene can be as high as 212 mA cm-2 and 536 mA cm-2 respectively from 1A and 1I (Figure. 4). These values correspond to a production of ~ 147.84 L and 369.6 L of ethylene per m2 per hour of electrode for their applied potentials of -3.55 V and -3.9 V, respectively.
  • Importantly the functionalization of Cu to obtain compounds according to the invention translates into 1) high activity (higher current density), 2) higher efficiency towards the conversion of CO2, 2) High activity towards the production of C2H4 product (Table 1).
  • The catalysts according to the invention prepared and tested in the example allowed improving the performance towards the production of C2H4 molecule at room temperature and atmospheric pressure. Compared to traditional Cu electrocatalyst, the Faradaic efficiency towards ethylene are increased by 43% and 49% for 1A and 1I groups modified Cu.
  • The new electrocatalysts according to the invention are more energy efficient.
    • List of references
    • [1] Bushuyev, O. S. et al. What should we make with CO2 and how can we make it? Joule 2, 825-832 (2018).
    • [2]. Ager, J. W. & Lapkin, A. A. Chemical storage of renewable energy. Science 360, 707-708 (2018).
    • [3]. Jouny, M., Luc, W. & Jiao, F. General techno-economic analysis of CO2 electrolysis systems. Industrial & Engineering Chemistry Research 57, 2165-2177 (2018).
    • [4]. Verma, S., Lu, S. & Kenis, P. J. Co-electrolysis of CO2 and glycerol as a pathway to carbon chemicals with improved technoeconomics due to low electricity consumption. Nature Energy 4, 466-474 (2019).

Claims (15)

  1. A process of manufacture of a catalyst compound comprising the steps of:
    a) electrodepositing copper on a porous gas diffusion layer, the porous gas diffusion layer being optionally pre-treated;
    b) functionalization of the metal catalyst obtained in step a) by contacting with a diazonium salt of formula I:
    Figure imgb0033
     wherein,
    - X- represents an anion,
    - a is an integer from 1 to 3,
    - ArA represents an aryl group, substituted by at least one -RA group,
    - -RA represents at least one substituent chosen from a halo group, - R1, -NO2, -OR1, -NR2R3 and a group of formula II:
    Figure imgb0034
     in which,
    ∘ -R1 represents a C1 to C3 alkyl group,
    ∘ -R2 and R3 independently represent H or a C1 to C3 alkyl group,
    ∘ b is an integer from 1 to 3,
    ∘ FB is a functional group chosen from -N=N- and -NH-,
    ∘ ArB represents an aryl group, substituted by at least one -RB group,
    ∘ -RB represents at least one substituent chosen from a halo group, -R1, -OR1 and -NR2R3,
    ∘
    Figure imgb0035
    represent the point of attachment to ArA.
  2. The process according to claim 1, wherein the copper is electrodeposited in a raspberry-like morphology.
  3. The process according to any of preceding claims, further comprising a pre-treatment step a') of electrodepositing Ag, Bi, Zn and/or Sn on the porous gas diffusion layer.
  4. The process according to any of preceding claims, wherein X- is chosen from BF4 -, Cl- and HSO4 -.
  5. The process according to any of preceding claims, wherein ArA and/or ArB are phenyl groups.
  6. The process according to any of preceding claims, wherein the diazonium salt of formula I is chosen from the following salts:
    Figure imgb0036
    Figure imgb0037
  7. The process according to any of preceding claims, further comprising a step c) of spray coating an ionomer of formula III:
    Figure imgb0038
     wherein,
    m and n are integers from 1 to 50,000.
  8. A catalyst compound obtained by the process according to any of the preceding claims.
  9. A catalyst compound comprising a porous gas diffusion layer, said porous gas diffusion layer being at least partially coated by copper atoms, wherein at least one copper atom is functionalised by a substituent of formula I':
    Figure imgb0039
     wherein ArA, RA and a are defined as in previous claims and
    Figure imgb0040
    represents the point of attachment to copper.
  10. The compound according to the preceding claim, further comprising a Ag, Bi, Zn and/or Sn atom layer in between the porous gas diffusion layer and the copper layer.
  11. The compound according to any of claims 8 to 10, wherein the copper is in a raspberry-like morphology.
  12. The compound according to any of claims 8 to 11, wherein the porous gas diffusion layer is a commercial conducting carbon-based gas diffusion electrode or a porous polymer substrate such as PTFE, nylon or PVDF.
  13. Use of the compound according to any of claims 8 to 12 as a catalyst, preferably to convert CO2 into small molecules, preferably C2H4, C2H5OH, CO, formic acid, as well as small amount of H2.
  14. A process of conversion of CO2 into small molecules comprising a step of contacting CO2 with a catalyst compound according to any of claims 8 to 12.
  15. The process according to the preceding claim, wherein the conversion reaction of CO2 is done under atmospheric pressure and at room temperature.
EP22305716.7A 2022-05-13 2022-05-13 Functionnalised copper electrochemical catalysts for conversion of co2 to small molecules Pending EP4276224A1 (en)

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Citations (2)

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US20060226021A1 (en) * 2002-12-20 2006-10-12 Heiko Brunner Mixture of oligomeric phenazinium compounds and acid bath for electrolytically depositing a copper deposit

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US20060226021A1 (en) * 2002-12-20 2006-10-12 Heiko Brunner Mixture of oligomeric phenazinium compounds and acid bath for electrolytically depositing a copper deposit
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Title
AGER, J. W.LAPKIN, A. A.: "Chemical storage of renewable energy", SCIENCE, vol. 360, 2018, pages 707 - 708
BUSHUYEV, O. S. ET AL.: "What should we make with C0 and how can we make it", JOULE, vol. 2, 2018, pages 825 - 832
CHIRA ANA ET AL: "Electrodeposited Organic Layers Formed from Aryl Diazonium Salts for Inhibition of Copper Corrosion", MATERIALS, vol. 10, no. 3, 1 January 2017 (2017-01-01), CH, pages 235, XP093011401, ISSN: 1996-1944, DOI: 10.3390/ma10030235 *
FAN LEI, XIA CHUAN, YANG FANGQI, WANG JUN, WANG HAOTIAN, LU YINGYING: "strategies in catalyst and electrolyzer design for electrochemical CO2 reduction toward C2+ productsproducts", SCIENCE ADVANCES, vol. 6, 21 February 2020 (2020-02-21), pages 1 - 17, XP009541564, DOI: 10.1126/sciadv.aay3111 *
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