IRON AND COBALT MOLECULAR COMPLEXES FOR THE SELECTIVE ELECTROCHEMICAL REDUCTION OF CO2 INTO CO, WITH FLOW CELLS

Abstract

The present invention concerns a flow cell electrolyzer (1) to electrochemically reduce reagent gas CO2 into gaseous CO, with an anodic compartment comprising an anode (2) with a current collector, and on the current collector, at least a catalyst to electrochemically oxidize H2O to O2, an anodic electrolyte solution (3) at a controlled flow rate Qa, comprising: a solvent, and an anodic electrolyte, the solvent being water at neutral or basic pH; a cathodic compartment comprising a cathodic electrolyte solution (6), at a controlled flow rate Qc, comprising: the solvent, and a cathodic electrolyte, the solvent being water at neutral or basic pH, a gas diffusion porous cathode (9) which comprises, on a gas diffusion porous current cathode collector which is electrochemically inert, at least a molecular catalyst on a surface S to electrochemically reduce CO2 into CO, with a by-production of H2, the molecular catalyst being chosen between the list with the metal chosen among: Iron, Cobalt: metal porphyrin with one or several +N(C1-C4 alkyl)3 groups, metal phthalocyanine, metal phthalocyanine with one or several +N(C1-C4 alkyl)3 groups, or cobalt quarter pyridine.

Description

FIELD OF THE INVENTION

The present invention relates to iron and cobalt molecular complexes as catalysts for the highly selective electrochemical reduction of CO₂ into CO, with electrochemical cells comprising them.

STATE OF ART

Despite the increasingly frequent use of renewable energies to produce electricity and avoid concomitant production of CO₂, it is reasonable to consider that CO₂ emissions, in particular resulting from energy production, will remain high in the next decades. Thus, it appears necessary to find ways to capture CO₂ gas, either for storing or valorization purposes.

Indeed, CO₂ can also be seen, not as a waste, but on the contrary as a source of carbon. For example, the promising production of synthetic fuels from CO₂ and water has been envisaged.

However, CO₂ exhibits low chemical reactivity: breaking its bonds requires an energy of 724 kJ/mol. Moreover, CO₂ electrochemical reduction to one electron occurs at a very negative potential, thus necessitating a high energy input, and leads to the formation of a highly energetic radical anion (CO₂^●−). Catalysis thus appears mandatory in order to reduce CO₂ and drive the process to multi-electronic and multi-proton reduction process, in order to obtain thermodynamically stable molecules. In addition, direct electrochemical reduction of CO₂ at inert electrodes is poorly selective, yielding formic acid in water, while it yields a mixture of oxalate, formate and carbon monoxide in low-acidity solvents such as DMF.

CO₂ electrochemical reduction thus requires catalytic activation in order to reduce the energy cost of processing, and increase the selectivity of the species formed in the reaction process.

Molecular catalysts that combine high selectivity and high current density for CO₂ electrochemical reduction to CO or other chemical feedstocks are in high demand. Molecular transition metal catalysts offer the distinct advantage of allowing for the fine-tuning of the primary and secondary coordination spheres by manipulating the chelating environment and the steric and electronic effects of the ligands. The ability to improve catalytic efficiency and product selectivity through the rational optimization of the ligand structure is a feature not accessible to the solid-state catalysts common to pilot-scale electrolyzer units.^1-2 There is now a range of known molecular catalysts, including those based on noble (e.g. Ru, Ir and Re) and earth-abundant metals (e.g. Co, Ni, Fe, Mn and Cu).^1-9 These catalysts typically trigger a two electron reduction of CO₂ to either CO or formate with reasonable efficiencies, but in organic solvents.

The integration of above described molecules by applying thin porous carbon films, such as carbon powder, carbon nanotubes or graphene to form hybrid catalytic materials, has proven to be a promising strategy to selectively achieve CO production in pure aqueous conditions. Reasonable performances have been obtained in nearly neutral conditions (pH 7-7.5) with good selectivity.^10,11 While these performances represent advances for CO₂RR (CO₂ reduction reaction) catalysts, much higher current densities are required for commercial operation, being highly selective and operating at low overpotentials at the same time. Moreover, these current densities remain far below those obtained with state-of-the-art solid-state Ag^12,13 or Au¹⁴ nanomaterials have been reported to reach >150 mA/cm².

SUMMARY OF THE INVENTION

Here, the invention presents a flow cell electrolyzer to electrochemically reduce a gas reactant comprising CO₂, into gaseous CO and gaseous H₂, with:

an anodic compartment comprising:

• • an anode with a current collector, and optionally on the current collector, at least a catalyst to electrochemically oxidize H₂O to O₂,
  • an anodic electrolyte solution, at a controlled flow rate Q_a, comprising: a solvent, and an anodic electrolyte, the solvent being water,
  • an anodic electrolyte solution inlet and an anodic electrolyte solution outlet connected to the anodic compartment, to circulate the anodic electrolyte solution;

a cathodic compartment comprising:

• • a cathodic electrolyte solution, at a controlled flow rate Q_c, comprising: a solvent, and a cathodic electrolyte, the solvent being water,
  • a gas diffusion porous cathode which comprises, on a gas diffusion porous current cathode collector which is electrochemically inert, at least a molecular catalyst incorporated in the porous cathode with a surface S, to electrochemically reduce the gas comprising CO₂, into gaseous CO with a by-production of gaseous H₂,the molecular catalyst being chosen between the list:
  • metal porphyrin with one or several ⁺N(C₁-C₄ alkyl)₃ groups, with the metal chosen among: Iron, Cobalt;
  • metal phthalocyanine, with the metal chosen among: Iron, Cobalt;
  • metal phthalocyanine with the metal chosen among: Iron, Cobalt, with one or several groups among: ³⁰ N(C₁-C₄ alkyl)₃, F, C(CH₃), or
  • cobalt quarter pyridine;

a channel for flowing the reagent gas CO₂, at a controlled flow rate Qg, onto or through the surface S of the gas diffusion porous current cathode collector;

a cathodic electrolyte solution inlet and a cathodic electrolyte solution outlet (8) connected to the cathodic compartment, to circulate the cathodic electrolyte solution, and the remaining reagent gas CO₂ and the product gas CO by the outlet;

an anion exchange membrane, impermeable to CO₂, CO, H₂ and O₂, between the anodic compartment and the cathodic compartment;

Pumping means serving to:

• • circulate by pumping the anodic electrolyte solution and the cathodic electrolyte solution between the inlet and the outlet,
  • flow by pumping the comprising gas CO₂ in the channel through the gas diffusion porous cathode; the pumping means being configured to control all flow rates of the cathodic and anodic electrolytes as well as the reagent gas CO₂ passing through the surface S of the gas diffusion porous cathode;

a power supply providing the energy necessary to trigger the electrochemical reactions involving the reagent.

At the anode, several oxidation reactions can occur, for instance:

• • the Oxygen Evolution Reaction, producing O₂ from H₂O, or
  • alcohol oxidation reactions.

The invention presents also a method of reducing a gas reactant comprising CO₂ into gazeous CO, with the flow cell electrolyzer comprising:

• • passing (diffusing or projecting) the flow of reagent gas CO₂, at a controlled flow rate Q_g, onto or through the surface S of the gas diffusion porous current diffusion electrode (GDE) of the cathodic compartment on which there is the molecular catalyst,
  • while the catholyte electrolyte solution circulates in between the Gas Diffusion Electrode and the anion exchange membrane, and

applying a potential to the Gas Diffusion Electrode.

BRIEF DESCRIPTION OF THE DRAWINGS

Other advantages and characteristics of the disclosed devices and methods will become apparent from reading the description, illustrated by the following figures, where:

FIG. 1. Current density and CO selectivity recorded at various potentials. Recorded in CO₂ saturated 0.5 M NaHCO₃ (pH 7.3). Each potential step was maintained for 20 min.

FIG. 2. Current density and CO selectivity recorded during a 24-hour electrolysis at −0.78 V vs RHE in CO₂ saturated 0.5 M NaHCO₃. The cell potential was 3.41 V.

FIG. 3. Applied potential and CO selectivity recorded under chronopotentiometric conditions at 50 mA·cm⁻² for 3 hours in CO₂ saturated 0.5 M NaHCO₃. The cell potential was 4.05 V.

FIG. 4. Applied potential and CO selectivity recorded under chronopotentiometric conditions at 50 mA·cm⁻² for 3 hours in CO₂ saturated 1.0 M NaHCO₃. The cell potential was 3.46 V.

FIG. 5. (A) Current density and CO selectivity at various cell temperatures. Recorded in CO₂ saturated 0.5 M NaHCO₃. (B) Arrhenius plot constructed from the TOF values calculated for each temperature step in (A).

FIG. 6. Current density and CO selectivity recorded at various potentials. Recorded in 1.0 M KOH solution (pH 14). Each potential step was maintained for 20 min.

FIG. 7. Applied potential and CO selectivity recorded under chronopotentiometric conditions at 27 mA·cm⁻² for 24 hours in 1.0 M KOH. The cell potential was 1.87 V.

FIG. 8. Applied potential and CO selectivity recorded under chronopotentiometric conditions at 50 mA·cm⁻² for 3 hours in 1.0 M KOH. The cell potential was 2.36 V.

FIG. 9. Step potential experiment, giving the current density recorded at various potentials. Recorded in CO₂ saturated 0.5 M NaHCO₃ (pH 7.3). Each potential step was maintained for 20 min.

FIG. 10. Step potential experiment, giving the current density recorded at various potentials. Recorded in argon saturated 0.5 M NaHCO₃ (pH 7.3) at a film formulated with the non-metalated porphyrin ligand. Each potential step was maintained for 20 min.

FIG. 11. Current density and CO selectivity recorded during a 6 hour electrolysis at −0.78 V vs RHE in CO₂ saturated 1 M NaHCO₃.

FIG. 12. Step potential experiment, giving the current density recorded at various potentials. Recorded in 1 M KOH (pH 14). Each potential step was maintained for 20 min.

FIG. 13. Step potential experiment, giving the current density recorded at various potentials. Recorded in 1 M KOH (pH 7.3) at a film formulated with the non-metalated porphyrin ligand. Each potential step was maintained for 20 min.

FIG. 14a. Cross-sectional view (a) and general scheme (b) of the CO₂ electrolyzer flow cell.

FIG. 14b. Scheme on the operation of the CO₂ electrolyzer flow cell of the present invention, which represents the stream (jet) of CO₂ projected on a Gas Diffusion Electrode.

FIG. 15. a: Current density for CO production as a function of the potential. b: Bulk electrolysis at fixed potential (E=−0.72 V vs. RHE) for CoPc2@carbon black deposited onto a carbon paper as cathodic material, in 1 M KOH. c: Co K-edge XANES profiles of CoPc2 (black dots), and CoPc2@carbon black before and after electrolysis (E=−0.72 V vs. RHE) which are superposed, in 1 M KOH solution.

FIG. 16. Flow cell electrolyzer set-up.

FIG. 17. Repetitive cyclic voltammetry for CoPc1@MWCNTs (bottom) and CoPc2@MWCNTs (top) films deposited onto a glassy carbon electrode (d=3 mm) in 0.5 M NaHCO₃ solution saturated with CO₂ (pH 7.3; black, 1^st scan; grey, 2^nd scan), at v=0.1 V s⁻¹.

FIG. 18. SEM image of a catalytic film deposited onto carbon paper.

FIG. 19. Blank experiments: Left, at E=−0.676 V vs. RHE) in the absence of catalyst in CO₂ saturated 0.5 M NaHCO₃ solution (pH=7.3); right, at E=−0.605 V vs. RHE with CoPc2@MWCNTs (1:15) in Ar saturated 0.5 M NaHCO₃ solution (pH=8.5). In both cases, only H₂ was detected as reaction product.

FIG. 20. Variation of the total current density as a function of the electrolysis potential at optimized mass ratio for CoPc1@MWCNTs in a CO₂ saturated solution containing 0.5 M NaHCO₃ (pH 7.3).

FIG. 21. Co 2p (left) and N 1s (right) XPS spectra before and after a 7 h electrolysis (E=−0.676 V vs. RHE) with CoPc2@MWCNTs with a 1:15 ratio in a CO₂ saturated solution with 0.5 M NaHCO₃ (pH 7.3).

FIG. 22. Bulk electrolysis at E=−0.971 V vs. RHE of a CO₂ saturated solution containing 0.5 M KCl (pH 4) using CoPc2@MWCNTs as catalyst.

FIG. 23. Total current density as a function of the applied potential for CoPc2@carbon black deposited onto a carbon paper as cathodic catalytic material, in 1 M KOH solution (flow cell device, see main text). Each potential step was held for a duration of 20 min.

FIG. 24. Top: K-space (insert) and Fourier transform EXAFS spectra of CoPc2@carbon black before (black) and after electrolysis (E=−0.72 V vs RHE) (grey) in 1 M KOH solution. Bottom: Co K-edge XANES spectra of the CoPc2@carbon black electrode after electrolysis (E=−0.72 V vs RHE) (red) together with those of reference compounds CoO (purple), CoOOH (orange), Co₃O₄ (blue) and metallic Co (green).

FIG. 25. Bulk electrolysis at fixed current density (75 mA cm⁻²) with CoPc2@carbon black deposited onto a carbon paper as cathodic catalytic material, in 1 M KOH solution (flow cell device, see main text). During the electrolysis, 2.5 g KOH were added every half hour into the cathode solution to maintain the pH balance.

FIG. 26. CO Selectivity as a function of time in hours at 50 mA/cm² with Co(qpy) catalyst in a zero gap cell device.

DETAILED DESCRIPTION

Inventors have developed a new flow cell electrolyzer that surprisingly allows an efficient reduction of CO₂ into gazeous CO with particularly high current densities and selectivity while operating at low overpotentials.

Accordingly, the present invention concerns: a flow cell electrolyzer 1 to electrochemically reduce a gas reactant (in a form of a stream projected on a GDE) comprising CO₂, into gaseous CO, with:

an anodic compartment comprising:

• • an anode 2 with a current collector, and, optionally, on the current collector, at least a catalyst to electrochemically oxidize H₂O to O₂,
  • an anodic electrolyte solution 3, at a controlled flow rate Q_a, comprising: a solvent, and an anodic electrolyte, the solvent being water, the anodic compartment being connected to an anodic electrolyte solution inlet 4 and an anodic electrolyte solution outlet 5;

a cathodic compartment comprising:

• • a cathodic electrolyte solution 6, at a controlled flow rate Q_c, comprising: a solvent, and a cathodic electrolyte, the solvent being water, the cathodic compartment being connected to a cathodic electrolyte solution inlet 7 and a cathodic electrolyte solution outlet 8,
  • a gas diffusion electrode 9 (porous cathode) comprising on an electrochemically inert gas diffusion porous current collector of surface S, at least a molecular catalyst to electrochemically reduce the gas flow comprising CO₂ into gaseous CO, with by-production of gaseous H₂ and O₂,

The cathodic electrolyte can comprise a phosphate buffer or potassium hydroxide, and the anodic electrolyte comprises a phosphate buffer or potassium hydroxide.

Also, the electrolyte can be sodium hydroxide NaOH (Nat) or cesium hydroxide CsOH (Cs⁺).

The cathodic electrolyte can comprise sodium hydroxide NaOH or cesium hydroxide CsOH and/or the anodic electrolyte comprises sodium hydroxide NaOH or cesium hydroxide CsOH.

The molecular catalyst is chosen in the list:

• • metal tetra phenyl porphyrin with at least one or several ⁺N(C₁-C₄ alkyl)₃ groups, with the metal chosen among: Iron, Cobalt; the other groups are independently selected from the group consisting of H, OH, F, C(CH₃);
  • metal phthalocyanine, with the metal chosen among: Iron, Cobalt;
  • metal phthalocyanine with the metal chosen among: Iron, Cobalt, with one or several groups among: ⁺N(C₁-C₄ alkyl)₃, F, C(CH₃)₃, the other groups are H;
  • cobalt quarter pyridine.

The flow cell electrolyzer 1 comprises also:

an anion exchange membrane 10, impermeable to CO₂, CO, H₂ and O₂, between the anodic compartment and the cathodic compartment;

a channel 11 for flowing the reagent gas CO₂, at a controlled flow rate Q_g, through the surface S of the gas diffusion porous current cathode collector;

a power supply providing the energy necessary to trigger the electrochemical reactions involving the reagent.

On the current collector of the anode, different reactions can occur. For instance:

at least one catalyst electrochemically oxidizes H₂O to O₂; or

at least one catalyst electrochemically oxidizes alcohols to organic compounds such as esters.

In the flow cell electrolyzer 1, all flow rates are controlled by passing the cathodic and anodic electrolytes as well as the reagent gas through pump means 12 serving to:

• • circulate by pumping the anodic electrolyte solution 3 and the cathodic electrolyte solution 6 between the inlets 4, and the outlets, 5,
  • flow by pumping the flow of reagent gas CO₂ onto or through the gas diffusion porous cathode 9;

In an example, the gas reactant comprises at least 99% per volume CO₂, or at least 99.5% per volume CO₂, or at least 99.9% per volume CO₂, or at least 99.99% per volume CO₂.

The flow cell 1 can have a device capable of recording the current generated by the electrochemical processes.

Advantageously, but in a non-limiting way, the channel for passing (diffuses or projects through or on the porous surface S of the GDE, the stream of CO₂) the reagent gas CO₂ can comprise a flow frame generating a turbulent flow.

Advantageously, but in a non-limiting way, pumping means 12 to recirculate the anodic electrolyte solution 3 and the cathodic electrolyte solution 6.

In a preferred embodiment, the anodic and/or cathodic electrolyte solution has a neutral pH (for instance a pH comprised between 6.5 and 7.5), or a basic pH.

In yet another preferred embodiment, the cathodic electrolyte solution has a basic pH. In such an embodiment, the anodic electrolyte solution may have an acidic or neutral pH.

In particular, the anodic electrolyte solution and/or the cathodic electrolyte solution has a pH from 9 to 14, preferably from 10 to 14, more preferably from 11.5 to 14, and more preferably from 13 to 14.

In yet another preferred embodiment, the cathodic electrolyte solution has a pH from 9 to 14, preferably from 10 to 14, more preferably from 11.5 to 14, and more preferably from 13 to 14. In such an embodiment, the anodic electrolyte solution may have an acidic or neutral pH.

Basic, i.e. alkaline conditions, in particular when applied to the cathodic electrolyte solution, allow operating the flow cell electrolyzer at surprisingly high current densities in comparison to acidic conditions.

The combination of basic conditions with the aforementioned molecular porphyrin, phthalocyanine or quarter pyridine catalysts further result in surprisingly high selectivities for the desired conversion of CO₂ to CO, with only minor or even no side product formation. Thus, with the high current densities and high CO selectivity, the invention allows production of close-to-pure CO from CO₂ at high throughput rates. The electrochemical reaction occurs at the triple phase interface between the catalyst (solid), the gaseous CO₂ (gas), and the catholyte (liquid). The use of gaseous CO₂ streaming through a porous cathode enables high current densities.

Furthermore, it was found that the aforementioned molecular catalysts demonstrate high long-term stability even at harsh alkaline pH conditions.

Further, the flow cell electrolyzer of the invention is effective under smooth conditions of temperature, pressure, and uses aqueous electrolytes. Such operating conditions are particularly advantageous in terms of, e.g., ease of use and energy consumption.

The electrochemical reduction of the reagent into CO can be carried out at ambient temperature. Also, in the flow cell electrolyzer 1 of the invention, the anodic and the cathodic electrolytes are at ambient temperature, In another realization mode, the anodic and the cathodic electrolytes are at ambient temperature are at a temperature higher than ambient temperature.

The electrochemical reduction of the reagent into CO can be carried out at atmospheric pressure. Also, in the flow cell electrolyzer 1 of the invention, the gas reactant flow is at atmospheric pressure. In another realization mode, the anodic and the cathodic electrolytes are at a pressure higher than atmospheric pressure.

Advantageously, the cathodic current collector can be carbon paper, stainless steel or other material. Advantageously, if it is on carbon paper, a composite multilayered porous current collector (for instance a polytetrafluoroethylene gas distribution layer) can be filed on the carbon paper to increase the reduction rate/efficiency.

In a realization, the porous cathode 9 comprises on the current collector an electrode film which, at least, contains polymers and the molecular catalysts. The electrode film can be filed in or grafted on the current collector.

Advantageously, when the molecular catalyst is a metal porphyrin, the metal porphyrin is a tetraphenylporphyrin which comprises specific groups on the phenyl moieties, with at least one or several ₊N(C₁-C₄ alkyl)₃ groups among specific groups.

In a first embodiment of the flow cell electrolyzer 1, the molecular catalyst is the iron porphyrin with the formula:

Wherein:

• • at least 1 and at most 8 groups among R₁ to R₁₀ and R_1′ to R_10′ being independently ⁺N(C₁-C₄ alkyl)₃ group,
  • the remaining groups R₁ to R₁₀ and R_1′ to R_10′ are independently selected from the group consisting of H, OH, F, C(CH₃)₃

In particular, the iron molecular catalyst can comprise:

the other groups among R₁ to R₁₀ and R_1′ to R_10′ are H; or

• • the other groups among R₁ to R₁₀ and R_1′ to R_10′ are H and F;

The iron molecular catalyst can comprise the ⁺N(C₁-C₄ alkyl)₃ groups in para or ortho position.

For instance: the molecular catalyst is an iron porphyrin FeTNT of formula (II):

Or chosen among these iron containing molecules:

preferably as its chloride salt.

With the iron porphyrin as molecular catalyst, at the operational conditions: the pH is between 7.3 and 14, and the potential applied to the cathode 9 is between 0 V and −1 V versus RHE (Reversible Hydrogen Electrode), the results of the flow cell can be: a current density for CO production of more than 5 and at least 150 mA·cm⁻², and the selectivity of the electrochemical reaction which is between 98% and 99.9%.

Also in a more particular embodiment, in the flow cell electrolyzer 1 according to the invention, with a tetra-phenyl iron porphyrin as a molecular catalyst:

the pH is between from 11.5 to 14, more preferably from 13 to 14,

the gas reactant flow passes at atmospheric pressure through the porous surface S of the gas diffusion electrode (GDE), and

the anodic and the cathodic electrolytes are at ambient temperature.

In a second embodiment of the flow cell electrolyzer 1, the flow cell electrolyzer 1 comprises the molecular catalyst which presents the formula:

wherein R₁ to R₁₆ are independently selected from the groups consisting of H, F, C(CH₃)₃ or ⁺N(C₁-C₄ alkyl)₃

In particular, R₁ to R₁₆ are H, and the molecular catalyst is a cobalt phthalocyanine CoPc of formula:

With the phthalocyanine as molecular catalyst, at the operational conditions: the pH is between 7.3 and 14, the potential applied to the cathode 9 is between −0.48 V and −0.98 V versus RHE, the results of the flow cell can be: a current density for CO production of more than 10 and at least 50 mAcm⁻², and a selectivity of the electrochemical reaction between 90% and 92%.

In another variant, the cobalt molecular catalyst presents at least 1 and at most 8 groups among R₁ to R₁₆ being independently ⁺N(C₁-C₄ alkyl)₃ group.

In another variant, the cobalt molecular catalyst presents for one or several of the specific following R₁, R₄, R₅, R₈, R₉, R₁₂, R₁₃ and R₁₆ groups, a ⁺N(C₁-C₄ alkyl)₃ substituent.

For instance, the molecular catalyst can be a cobalt phthalocyanine CoPc2 of formula:

or the molecular catalyst is a cobalt phthalocyanine CoPc3 of formula:

With the cobalt phthalocyanine with one or several ⁺N(C₁-C₄ alkyl)₃ groups, as molecular catalyst, at the operational conditions: the pH is between 7.3 and 14, and the potential applied to the cathode 9 is between −0.3 V and −1 V versus RHE, the results of the flow cell can be: a current density for CO production of more than 10 and at least 150 mAcm⁻², and a selectivity of the electrochemical reaction is between 92% and 96%.

Also, in a more particular embodiment, in the flow cell electrolyzer 1 according to the invention, with a cobalt phthalocyanine as a molecular catalyst, wherein:

the pH is between from 11.5 to 14, more preferably from 13 to 14,

the gas reactant flow passes at atmospheric pressure through the porous surface S of the gas diffusion electrode (GDE), and

the anodic and the cathodic electrolytes are at ambient temperature.

In an even more particular embodiment, in the flow cell electrolyzer 1 according to the invention, with a cobalt phthalocyanine with one or several ⁺N(C₁-C₄ alkyl)₃ groups, wherein:

the pH is between from 11.5 to 14, more preferably from 13 to 14,

the gas reactant flow passes at atmospheric pressure through the porous surface S of the gas diffusion electrode (GDE), and

the anodic and the cathodic electrolytes are at ambient temperature.

In a third embodiment of the flow cell electrolyzer 1, the flow cell electrolyzer 1 comprises the molecular catalyst which presents the formulae of the cobalt quarter pyridine

With the cobalt quarter pyridine as molecular catalyst, at the operational conditions: the pH is between 7.3 and 14, and the potential applied to the cathode 9 is between −0.6 V and −1 V versus RHE, the results of the flow cell can be: a current density for CO production is between 25 and 200 mAcm⁻², and the selectivity of the electrochemical reaction is between 86.1% and 98.8%.

In a particular embodiment, in the flow cell electrolyzer 1 according to the invention, with a cobalt quarter pyridine as molecular catalyst, wherein:

the pH is between from 11.5 to 14, more preferably from 13 to 14,

the gas reactant flow passes at atmospheric pressure through the porous surface S of the gas diffusion electrode (GDE), and

the anodic and the cathodic electrolytes are at ambient temperature.

As shown in the experimental section, flow cell electrolyzer of the invention allows an efficient reduction of CO₂ into gazeous CO with particularly high current densities and selectivity while operating at low overpotentials. Without wishing to be bound by any theory, this could stem from the fact that the reaction occurs at the triple phase interface between the molecular catalyst supported on the electrode (solid), the reagent CO₂ (gas) and the electrolyte solution (liquid).

Invention also relates to a method of reducing a gas reactant comprising CO₂ into gazeous CO, said method comprising, in a flow cell electrolyzer 1 as defined above:

• • passing the flow of reagent gas CO₂, at a controlled flow rate Q_g, onto or through the surface S of the gas diffusion porous current diffusion electrode (GDE) of the cathodic compartment on which there is the molecular catalyst,while the cathodic electrolyte solution 6 circulates in between the Gas Diffusion Electrode 9 and the anion exchange membrane 10, and
  • applying a potential at the Gas Diffusion Electrode 9.

In an embodiment, in said method, the anodic and/or cathodic electrolyte solution has a neutral (e.g. comprised between 6.5 and 7.5) or a basic pH. In a particular embodiment, the anodic electrolyte solution and/or the cathodic electrolyte solution has a pH comprised from between 9 to 14, preferably from 10 to 14, more preferably from 11.5 to 14, and even more preferably from 13 to 14.

In another embodiment, in said method, the gaz reactant flow is at atmospheric pressure. In another embodiment the gas reactant flow is at a pressure higher than atmospheric pressure.

In an embodiment, in the method according to the invention, the anodic and the cathodic electrolytes are at ambient temperature. In another embodiment, the anodic and the cathodic electrolytes are at a temperature higher than ambient temperatures.

The flow cell electrolyzer of the invention allows to combine high selectivity and high current density for CO₂ electrochemical reduction to CO. Accordingly, in an embodiment, in the method of the invention the potential applied to the Gas Diffusion Electrode 9 of the flow cell electrolyzer of the invention is of:

between 0 V and −1 V versus RHE, when the molecular catalyst is a tetra-phenyl iron porphyrin, thereby generating a current density for CO production of at least 150 mA·cm⁻²;

between 0.48 V and −0.98 V versus RHE when the molecular catalyst is a metal phthalocyanine, thereby generating a current density for CO production of at least 50 mA·cm⁻²;

between −0.3 V and −1 V versus RHE when the molecular catalyst is a cobalt phthalocyanine with one or several ⁺N(C₁-C₄ alkyl)₃ groups, thereby generating a current density for CO production of at least 150 mA·cm-2;

between −0.6 V and −1 V versus RHE when the molecular catalyst is a cobalt quarter pyridine with one or several ⁺N(C₁-C₄ alkyl)₃ groups, thereby generating a current density for CO production of at least 150 mA·cm⁻²

In another particular embodiment, when the potential applied to the Gas Diffusion Electrode 9 of the flow cell electrolyzer of the invention is of between 0 V and −1 V versus RHE, when the molecular catalyst is a tetra-phenyl iron porphyrin, said potential is not 0 V, thereby generating a current density for CO production of at least 150 mA·cm⁻².

In a more particular embodiment, in said method:

when the molecular catalyst is a tetra-phenyl iron porphyrin, the selectivity of the electrochemical reaction is between 98% and 99.9%;

when the molecular catalyst a metal phthalocyanine, the selectivity of the electrochemical reaction is between 90% and 92%;

when the molecular catalyst is a cobalt phthalocyanine with one or several ⁺N(C₁-C₄ alkyl)₃ groups,

the selectivity of the electrochemical reaction is between 92% and 96%;

when the molecular catalyst is a cobalt quarter pyridine with one or several ⁺N(C₁-C₄ alkyl)₃ the selectivity of the electrochemical reaction is between 86.1% and 98.8%.

First Embodiment

Preparation of the Hybrid Materials for the Gas Diffusion Electrode with FeTNT

7.2 mg carbon black was dispersed in 8 mL ethanol by sonication for 30 min. A solution of 2.08 mg FeTNT in 2 mL ethanol was added to the carbon black suspension followed by sonication for 30 min. 20 μL of a 5% w/w Nafion solution was added followed by sonication for 30 min. The as prepared ink was disposed at 65° C. on carbon paper masked with a PTFE frame to obtain a 1×1 cm² gas diffusion current collector.

Results

The inventors included FeTNT into a flow cell setup comprising FeTNT supported on a gas diffusion electrode as the cathode 9. Details of the setup are provided in the Supporting Information (see also FIGS. 14 and 16). Briefly, the electrolyzer consists of a sandwich of flow frames, electrodes, gaskets and an ion exchange membrane 10, which were assembled as schematically illustrated in FIG. 14a. A gas flow of CO₂ is delivered from the back side of the cathodic compartment and flows through the gas diffusion electrode (GDE), while the catholyte solution is circulated in between the GDE and the anion exchange membrane 10 (AEM). On the other side of the AEM, the anolyte is directed between the AEM and the Pt/Ti alloy anode 2, FIG. 14b. FeTNT was dispersed in a colloidal ink with carbon black and subsequently deposited on the carbon fiber paper, composing the cathode 9.

A survey of the catalytic activity as a function of applied potential was first performed in CO₂ saturated 0.5 M NaHCO₃. FIG. 1 illustrates the increase in current density recorded for the CO₂RR as the overpotential was gradually set to more negative values by steps of 100 mV, along with the selectivity for CO production (see also FIG. 9). Initially, at the less negative potentials, CO was detected as the only product; whereas minor amounts of H₂ stemming from the HER (Hydrogen Evolution Reaction) was observed at more negative potentials. The small amounts of the latter, even at potentials well beyond the HER onset, reflects the ability of the catalyst to strongly suppress the HER in favour of CO production. This was further verified by employing a non-catalytic film in the electrolyzer, i.e., a film formulated with the non-metalated porphyrin ligand, resulting in H₂ production exclusively (see FIG. 10). The average current density and the CO selectivity at each applied potential is collected in Table 1 hereafter.

TABLE 1
Current densities and CO selectivity obtained with a catalytic film
with FeTNT as catalyst (pH 7.3) as a function of the potential
applied at the cathode 9.
E/V vs RHE	jav/mAcm−2	% CO
−0.38	7.2	99.9
−0.48	9.8	99.9
−0.58	14.8	99.8
−0.68	20.7	99.5
−0.78	27.2	99.3
−0.88	34.9	98.9
−0.98	42.1	98.6

The endurance of the catalytic film was tested by performing a chronoamperometric electrolysis for 24 hours. Based on the values listed in Table 1, a potential of −0.78 V vs RHE was chosen as this potential compromises between high current density and the ability of the catalyst to provide a nearly perfect CO production. The current density and the CO selectivity that have been obtained are shown in FIG. 2, demonstrating the excellent stability of the system: a current density of 27.3 mAcm⁻² was maintained through the experiment with an average selectivity for CO of 98.2±0.2%.

Under the same conditions, the cell performance was further evaluated by performing a chronopotentiometric electrolysis at a current density of 50 mAcm⁻². As shown in FIG. 3, the cell maintained this current value for 3 hours at a potential of −1.14 V vs RHE. The product selectivity was not affected by the almost 2-fold current density increase, as CO was produced with a 98.3±0.3% average selectivity.

In order to diminish the cell potential, the ohmic resistance of the cell was reduced by increasing the electrolyte concentration. This was demonstrated in a 1.0 M NaHCO₃ electrolyte solution, where a gain of >8 mAcm⁻² was obtained at an applied potential of −0.78 V vs RHE, without compromising the CO selectivity (see FIG. 11). In a chronopotentiometric electrolysis, see FIG. 4, the applied potential at 50 mAcm⁻² shifted positively to −0.86 V vs RHE, and in addition the cell potential was reduced by 590 mV. The CO product selectivity was 99.0±0.2% on average.

A complementary approach to boost the cell performance was achieved by thermally activating the catalyst. During a chronoamperometric electrolysis at −0.78 V vs RHE, the catholyte temperature was incrementally increased from 24° C. to 34° C. and finally to 40° C. As shown in FIG. 5A, an increase in current density was observed upon increasing the temperature, while maintaining the high CO product selectivity. Taking the TOF (in s⁻¹) as an apparent 1^st order rate constant for the CO₂ conversion (assuming steady state conditions for the catalyst and proton source), an Arrhenius plot: In(TOF) vs 1/T (in K⁻¹) was constructed (FIG. 5B). From the slope, the activation energy, Ea, was calculated to 12 kJmol⁻¹.

In alkaline conditions (1.0 M KOH, pH 14) the cell performance was drastically improved. FIG. 6 shows the resulting current densities and CO product selectivity recorded at various potentials (see also FIG. 12). A current density of 6 mAcm⁻² was observed at 0.014 V vs RHE, and 155 mAcm⁻² was reached at −0.59 V vs RHE, with an excellent CO product selectivity, as summarized in Table 2. In a control experiment with the non-metalated porphyrin ligand, H₂ was the only detected product (see FIG. 13).

TABLE 2
Current densities and CO selectivity obtained with a catalytic film
with FeTNT as catalyst (pH 14) as a function of the potential
applied at the cathode 9.
E/V vs RHE	jav/mAcm−2	% CO
0.014	6.0	99.9
−0.086	16.5	99.9
−0.19	37.6	99.9
−0.29	62.9	99.8
−0.39	89.7	99.5
−0.49	122.4	99.2
−0.59	155.2	98.1

To investigate the endurance of the catalyst in alkaline conditions, a chronopotentiometric electrolysis was performed at 27 mAcm⁻² for 24 h, the same current density value as performed in pH-neutral conditions. As shown in FIG. 7, a potential of ca. −0.16 V vs RHE was measured over the 24 hour course, showing only a minute increase. The CO product selectivity remained extremely high: 99.7±0.2% on average.

For a direct comparison with the pH-neutral 1.0 M bicarbonate system, a chronopotentiometric electrolysis was performed at 50 mAcm⁻² in 1.0 M KOH, as shown in FIG. 8. Over the course a 3 hours electrolysis, the applied potential remained stable (−0.23 V vs RHE), a very weakly negative potential for such high current density. Again, the CO selectivity was nearly perfect, with an average value of 99.8±0.1%.

Second Embodiment

The inventors included CoPc2 into the same flow cell setup described in the first embodiment. CoPc2 was supported on a gas diffusion electrode as the cathode 9. Details of the setup are provided in the Supporting Information (see FIG. 16). CoPc2 was dispersed in a colloidal ink with carbon black and subsequently deposited on the carbon fiber paper, composing the cathode 9.

At −0.3 V vs. RHE and pH 14 (1 M KOH for the electrolyte), which corresponds to a low 200 mV overpotential, a high current density with j_CO=22.2 mA/cm² was achieved (j_CO is the partial current density for CO production). The dependence of the current density for CO production is reported in FIG. 15a (see also FIG. 22). Upon setting the electrolysis potential at −0.72 V vs. RHE, j_CO raised to 111.6 mA/cm² with 96% selectivity, while excellent stability over the course of the 3 h electrolysis was obtained (FIG. 15b). The only additional gas phase by-product was H₂ (4% selectivity) and the catholyte solution was carefully checked by ¹H NMR; no formate nor methanol was detected during the experiment. The obtained j_CO corresponds to a turnover frequency (TOF) of 2.7 s⁻¹ and a turnover number (TON) of 29008. A maximum current density of 165 mA cm⁻² for CO generation was obtained at −0.92 V vs. RHE. Long term stability of the catalytic material was assessed upon applying a constant current density of 75 mA cm⁻² for 10 h, which led to a cathodic potential of −0.65 V vs. RHE (h=540 mV) with 94% selectivity of CO (j_CO=70.5 mA cm′) (FIG. 23). All the collected data are compiled in Table 3, along with a comparison of previously reported catalysts. The type of cell used (H cell vs. flow cell) is also indicated to ease comparison between data. The Co K-edge XANES spectra of CoPc2@carbon black were recorded before and after electrocatalysis at E=−0.72 V vs. RHE. FIG. 15c shows these spectra together with that of the starting CoPc2 complex. All these spectra present the typical features expected for a cobalt(II) phthalocyanine complex, i.e. a low intensity pre-edge peak at 7111 eV (corresponding to a 1s to 3d/4p transition) and a shoulder at 7717 eV (corresponding to a 1s to 4p_z transition). Interestingly, the intensity of these two transitions were shown by Li et al¹⁷ to depend on the attachment to a surface, i.e. the pre-edge intensity increases and the shoulder decreases upon adsorption onto nanotubes, respectively. The same trend is observed in the CoPc2@carbon black system, with decreased pre-edge and increased shoulder intensities on going from the starting complex to the adsorbed species. This trend continues after catalysis, suggesting an even closer interaction with the surface while maintaining the overall structure of the molecular catalyst after the experiment. This structural conservation is further confirmed by the EXAFS spectra (FIG. 24), which also present the typical features of a cobalt phthalocyanine complex.³⁸ In addition, comparison of the spectrum of CoPc2@carbon black recorded after catalysis with those of reference cobalt samples (FIG. 24) clearly shows that the changes observed on the spectrum after catalysis are insignificant as far as the overall structure is concerned.

Remarkably, CoPc2 remains highly selective for the CO₂-to-CO conversion across an interval of 10 units of pH, extending from acidic (pH 4) to basic solutions (pH 14). An averaged 92% selectivity for CO₂ reduction with partial current density of ca. 20 mA cm⁻² were routinely obtained in the whole domain of pH values with excellent stability over time. In close to neutral solutions (pH 7.3), CoPc2 is a significantly better catalyst than the non-substituted phthalocyanine CoPc (see Table 3, entries 2 and 3) with a ca. 25% increase in current density at similar overpotential, but it also surpasses state-of-the art tetra-cyano substituted phthalocyanine (CoPc-CN, Table 3, entry 4) and unsubstituted Co phthalocyanine polymerized around carbon nanotubes (CoPpc, Table 3, entry 5), both in terms of current density and turnover frequency. Similarly to the previously reported cobalt phthalocyanines mentioned above, CoPc2 exhibits excellent stability over time, showing a 10.5 h electrolysis experiment, with no loss of performance.

TABLE 3
Comparison of electrolysis performances between CoPc2@carbon powder
hybrid catalyst and previously reported state-of-the art immobilized molecular
Co catalysts and Ag nanomaterial.
		E (V vs. RHE)		jCO		CO
		[overpotential		(mA	TOF	sel.	Cell
Entry	Catalyst	(mV)]	Electrolyte	cm−2)	(s−1)	(%)	type	Ref.
1	CoPc2	−0.97	0.5M KCl	16.3	6.1	92	H-cell	this work
		[836]a
2	CoPc2	−0.675	0.5M	18.1	6.8	93	H-cell	this work
		[539]a	NaHCO3
3	CoPc	−0.675	0.5M	13.1	4.1	92	H-cell	this work
		[546]a	NaHCO3
4	CoPc-CN	−0.63	0.1M	14.7	4.1	98	H-cell	15
		[520]	KHCO3
5	CoPpc	−0.61	0.5M	18	1.4	ca. 90	H-cell	16
		[500]	NaHCO3
6	Coqpy	−0.55	0.5M	19.9	12	99	H-cell	10
		[440]	NaHCO3
7	CoPc2	−0.31	1M KOH	22.2	0.54	93	Flow-cell	this work
		[200]b
8	CoPc2	−0.65	1M KOH	70.5	1.67	94	Flow-cell	this work
		[540]b
9	CoPc2	−0.72	1M KOH	111.6	2.7	96	Flow-cell	this work
		[610]b
10	CoPc2	−0.92	1M KOH	165	3.9	94	Flow-cell	this work
		[810]b
11	CoPc-CN	−0.66	1M KOH	31	/	94	Flow-cell	11
		[550]
12	Agc	−0.81	1M KOH	156.5	/	92	Flow-cell	13
		[700]
Entry 1: Γ = 14.4 nmol cm−2 (pH 4, 2 h electrolysis),
entry 2: Γ = 14.4 nmol cm−2 (pH 7.3, 1 h electrolysis),
entry 3: Γ = 23.3 nmol cm−2 (pH 7.3, 1 h electrolysis),
entries 7-10: Γ = 0.216 μmol cm−2 (pH 14, for 0.5, 10, 3 and 0.3 h electrolysis respectively). Typical uncertainty on jCO and TOF values is ± 5%.
acorrected from ohmic drop (uncompensated solution resistance of ca. 3 W, electrode surface 0.5 cm2)
buncorrected from ohmic drop
ccarbonate-derived Ag nano-catalyst (500 nm thickness), see reference 13 for details.

A turnover frequency up to 6.8 s⁻¹ was reached and, generally, a very small loading of the catalysts was necessary to obtain high j_CO (see for example Table 3, entries 1-2). Long term electrolysis (10 h) in basic conditions (pH 14) at −0.65 V vs. RHE led to an average j_CO close 70.5 mAcm⁻² and also illustrates the remarkable stability of the cobalt catalyst. The ability to implement CoPc2 in various pH conditions is also a key feature that may allow for combining the Co catalyst to various types of anodic materials in order to decrease the overall cell potential. In particular, the excellent performance obtained at pH 14 should permit to pair the CoPc2 loaded cathode 9 with the most efficient oxygen evolving metal oxide anode 2 materials. At this pH, CoPc2 matches the state-of-the art Ag based catalyst sputtered onto a PTFE membrane, both in terms of selectivity and current density (Table 3, compare entries 10 and 12).

Upon introducing a positively charged trimethylammonium group on the parent cobalt phthalocyanine, a highly efficient and versatile catalyst for the CO₂-to-CO electrochemical conversion in water has been obtained. Furthermore, it operates with high selectivity (92 to 96%) in a broad range of pHs, extending from acidic (pH 4) to basic conditions (pH 14). In acid and neutral conditions, current densities close to 20 mA cm⁻² were routinely obtained. In a 1 M KOH electrolyte solution, same current densities could be obtained at a very low overpotential of 200 mV, once the hybrid catalyst mixed with carbon support was included in a gas flow cell. At −0.92 V vs. RHE, a partial current for CO production of 165 mAcm⁻² was found with 94% catalytic selectivity. These performances show that hybrid catalytic materials including only carbon and an earth abundant metal based molecular complex can rival noble metal nanomaterials such as Ag and Au. This study highlights that rational tuning of the structure of simple metal complexes may allow for high performance, and it is likely that further improvement is yet to come. Finally, this work opens new perspectives for the development of low-cost catalytic materials to be included in CO₂ electrolysers.

Supplementary Information

Methods

All electrocatalytic reactions were carried out under an atmosphere of argon or CO₂. Chemicals, including CoPc1 and supporting electrolytes were obtained from commercial suppliers. Supplementary Information section describes the synthesis and characterization of CoPc2 and FeTNT, as well as typical protocols for electrocatalytic CO₂ reduction.

Typical protocol for electrocatalytic CO₂ reduction. After preparation of a catalytic ink containing either FeTNT, CoPc1 or CoPc2, and deposition of the material onto porous carbon paper, controlled potential electrolysis were performed either in a closed electrochemical cell or in a flow cell electrolyser using a PARSTAT 4000 potentiostat (Princeton Applied Research). Gas chromatography analyses of gas evolved in the headspace during the electrolysis were performed with an Agilent Technologies 7820A GC system equipped with a thermal conductivity detector. Conditions allowed detection of both H₂, O₂, N₂, CO, and CO₂. Calibration curves for H₂ and CO were determined separately by injecting known quantities of pure gas

General Considerations

Chemicals and Characterization Methods

Chemicals and materials were purchased from Sigma-Aldrich, Fluka, TCI America, ABCR or Alfa Aesar, and used as received. All aqueous solutions were prepared with Millipore water (18.2 MO cm). The MWCNTs were purchased from Sigma-Aldrich (O.D.×L 6-9 nm×5 μm, >95%). The cobalt (II) phthalocyanine (CoPc1) ((3-form, dye content 97%) was purchased from Sigma-Aldrich. Toray Carbon Paper (CAS Number: 7782-42-5), TGP-H-60, 19×19 cm was purchased from Alfa Aesar and used for preparation of the cathode 9s for the electrochemical cell. The cathode 9s (gas diffusion electrodes) used in the flow cell were prepared using Freudenberg C24H5 carbon paper (21×29.7 cm, product code FSGDL). VULCAN® XC72R Speciality Carbon Black was purchased from Cabot Corporation.

4-tert-butylphthalonitrile was obtained from TCI America. 3-nitrophthalonitrile was purchased from ABCR. All solvents were of synthetic grade. Infrared spectra (IR) were recorded on a Bio-Rad FTS 175C FTIR spectrophotometer. UV-visible absorption spectra were obtained using a Shimadzu 2001 UV spectrophotometer. High resolution mass spectra were measured on an Agilent 6530 Accurate-Mass Q-TOF LC/MS spectrometer equipped with electrospray ionization (ESI) source. NMR spectra were recorded in deuterated chloroform (CDCl₃) and THF-d₈ on a Varian 500 MHz spectrometer. Melting points were recorded on a Stuart SMP apparatus.

Synthesis of FeTNT

A solution of 5,10,15,20-tetrakis(4-trimethylammonio-phenyl)porphyrin tetrachloride (250 mg, 0.253 mmol, 1 eq) in water (500 mL) is prepared and put under argon flux, Mohr's salt is added to the solution (810 mg, 3.75 mmol, 15 eq) and the solution is heated to 85° C. for 4 h. Ammonium hexafluorophosphate (2.5 g, 15 mmol, 60 eq) is added and the obtained precipitate is separated by centrifugation (10000 rpm, 30 min). The red solid obtained is rinsed one time in pure water and separated again by centrifugation (10000 rpm 30 min), then rinsed one time in 1 to 1 mixture of chloroform and acetone and separated by centrifugation (10000 rpm 30 min). Residual solvent is evaporated under Argon flux. Yield: 92% (343 mg)

UV-Vis (DMF): λ_max nm (log ε) 407 (4), 568 (4.98).

Cobalt catalyst CoPc2 was prepared as illustrated here:

Synthesis of Phthalonitrile and Phthalocyanines

Synthesis of 3-(dimethylamino)phthalonitrile 1

3-Nitrophthalonitrile (2 g, 11.5 mmol) and dimethylamine hydrochloride (2.8 g, 34.6 mmol) were dissolved in anhydrous DMF (30 mL) under argon atmosphere then finely powdered dry potassium carbonate (30 g, 217.5 mmol) was added portion-wise over 15 min. The reaction mixture was stirred under argon at 65° C. for 24 h then poured into water (250 mL). The resulting solid was collected by filtration and washed with water. After drying in vacuum, the crude product was recrystallized from ethanol. Yield: 80% (1.57 g). m.p. 105° C. ¹H NMR (500 MHz, CDCl₃): δ, ppm 3.18 (s, 6H), 7.12 (d, 1H), 7.15 (d, 1H), 7.46 (t, 1H). ¹³C NMR (125 MHz, CDCl₃): δ, ppm 172.4, 155.4, 133.1, 123.0, 120.5, 118.0, 116.6, 116.3, 110.0, 100.6, 42.7. FT-IR (v, cm⁻¹): 2992, 2937, 2874, 2203, 1584, 1486, 1425, 1357, 1244, 1192, 1122, 1008, 792, 722.

Synthesis of Phthalocyanine 3

Granules of lithium were added to anhydrous n-pentanol (10 mL). This mixture was heated to 60° C. under argon flux until total consumption of the granules. 3-(dimethylamino)phthalonitrile 1 (0.25 g, 1.46 mmol) and 4-tert-butylphthalonitrile 2 (3.2 g, 17.52 mmol) were then added and this reaction mixture was refluxed for 18 h, then cooled to room temperature and poured to an ethanol/water mixture. The resulting dark blue-green precipitate was filtered off, washed several times with water and dried. Phthalocyanine 3 was isolated from this crude mixture of phthalocyanines by chromatography on silica gel using a mixture of CH₂Cl₂/EtOH (100:1) as the eluent. The tetra-tert-butylphthalocyanine 4 was first eluted and the phthalocyanine 3 was the second eluted compound. Yield: 15% (160 mg). ¹H NMR (500 MHz, THF-d₈): δ, ppm −2.04 (s, 1H), −1.95 (s, 1H), 1.84 (m, 10H), 1.88-1.94 (m, 17H), 3.70 (s, 3H), 7.45 (d, 1H), 7.79 (m, 1H), 8.10-8.40 (m, 4H), 8.61 (d, 1H), 8.85-8.91 (m, 1H), 8.98-9.24 (m, 4H), ¹³C NMR (125 MHz, THF-d₈): δ, ppm 152.97, 152.94, 152.88, 152.84, 152.61, 152.58, 150.16, 150.12, 133.67, 129.92, 127.43, 127.30, 127.22, 126.75, 125.50, 122.12, 122.07, 121.93, 121.90, 121.77, 118.69, 118.65, 118.51, 118.48, 118.41, 117.87, 117.83, 114.74, 78.54, 78.28, 78.02, 44.36, 39.98, 37.15, 37.06, 35.67, 35.60, 35.50, 31.89, 31.43, 31.32, 29.65, 29.32, 22.58, 13.43. ESI-HRMS: m/z 726.4030 [M]⁺ calculated for C₄₆H₄₇N₈: 725.95. UV-vis (DMF): λ_max nm (log ε) 346 (3.90), 689 (4.87), 718 (5.38). FT-IR (v, cm⁻¹): 3288, 2955, 2863, 2776, 1618, 1501, 1316, 1186, 1014, 828, 742.

Synthesis of Phthalocyanine 5

A mixture of phthalocyanine 3 (50 mg, 0.06 mmol), CoCl₂ (18 mg, 0.12 mmol), and DBU (1 mL) in dried n-pentanol (5 mL) was heated to reflux for 18 h under argon. After cooling to room temperature, the reaction mixture was poured into an ethanol/water mixture. The resulting precipitate was filtered off and washed several times with water. Phthalocyanine 5 was purified by chromatography on silica gel using a mixture of CH₂Cl₂/EtOH (50:1) as the eluent. Yield: 75% (35 mg). ESI-HRMS: m/z 782.3234 [M]⁺ calculated for C₄₆H₄₅CoN₉: 782.86. UV-vis (DMF): λ_max nm (log ε) 332 (3.70), 693 (4.74); FT-IR (v, cm⁻¹): 2955, 2856, 1606, 1457, 1316, 1254, 1094, 804, 737.

Synthesis of phthalocyanine CoPc2

Phthalocyanine 5 (35 mg, 0.044 mmol) was dissolved in DMF (5 mL), and methyl iodide (0.2 g, 1.5 mmol) was added. The mixture was stirred at room temperature for 16 h then poured into diethyl ether (25 mL). The resulting blue precipitate was filtered off, washed with ether and dried. Yield: 32 mg (88%). ESI-HRMS: m/z 797.3668 [M]⁺ calculated for C₄₇H₄₈CoN₈: 797.90. Anal. calcd for C₄₇H₅₈ColN₉O₅ (CoPc2.5H₂O): C, 55.28; H, 5.98; N, 11.88. Found: C, 55.62; H, 5.76; N, 12.42. UV-vis (DMF): λ_max nm (log ε) 326 (4.41), 664 (4.65). FT-IR (v, cm⁻¹) 3047, 2949, 2851, 1655, 1606, 1476, 1328, 1254, 1088, 933, 829, 749.

Preparation of the Hybrid Materials

For CV experiments and electrolysis in the closed electrolysis cell, 3 mg of MWCNTs were dispersed in 2 mL ethylene glycol (EG)/ethanol (EtOH) 1:1 (v/v) mixture followed by 30 min of sonication. 1 mg of the cobalt catalyst (CoPc1, CoPc2) was dissolved in 1 mL EG/EtOH mixture. Various volumes of this solution were added to the MWCNTs suspension in a total volume of 3 mL, so as to get mass ratio (1:6, 1:15 and 1:30) of the catalyst. The suspension was further sonicated for 30 min. Finally, Nafion® was added (2.9%, 30 μL) and the complete mixture was sonicated for 30 min to obtain the final catalytic ink.

For the flow cell set-up, 3 mg of carbon black were dispersed in 3 mL EtOH followed by 30 min of sonication. 0.2 mg of CoPc2 was dissolved in 1 mL EtOH so as to get a mass ratio (1:15) of the catalyst. The suspension was further sonicated for 30 min. Finally, Nafion® was added (2.9%, 30 μL) and the complete mixture was sonicated for 30 min to obtain the final catalytic ink. The ink was drop casted on carbon paper masked with a Teflon frame to obtain an electrode area of 1×1 cm².

Electrochemical Studies

Controlled potential electrolyses were performed using a PARSTAT 4000 potentiostat (Princeton Applied Research).

Preparative Scale Electrolysis

In the closed cell, experiments were carried out in a cell using a Toray carbon paper as working electrode, and a SCE reference electrode closely positioned one from the other. The Pt grid counter electrode was separated from the cathodic compartment with a glass frit. The catalytic ink was dropped on one face of the Toray carbon paper cathode 9 (100 μL for a 0.5 cm² electrode), and allowed to dry under ambient conditions prior to use. The full cell setup was identical to the one used previously.¹⁸

The flow cell electrolyzer 1 (Micro Flow Cell® purchased by Electrocell) is composed by a sandwich of flow frames, electrodes, gaskets and a membrane, which, when assembled as illustrated in FIG. 14, constitute a three-compartment flow cell. One compartment delivers the CO₂ (at 16.7 sccm) from the back side and through the gas diffusion electrode (GDE, 1×1 cm², fixated in a Pt frame), while another directs the catholyte solution (1 M KOH, flow rate of 16 sccm) in between the GDE and the anion exchange membrane 10 (AEM, Sustainion™ X37-50). On the other side of the latter, the anolyte (1 M KOH, flow rate of 16 sccm) is directed between the AEM and the Pt/Ti alloy anode 2. The flow frames are made of PTFE, and the gaskets of peroxide cured EDPM. Catholyte and anolyte were recycled using peristaltic pumps. All tubings were made of PTFE and connected to the cell with PEEK ferrules and fittings. The whole setup is schematically shown below (FIG. 16).

Gas Detection

Gas chromatography analyses of gas sampled from the headspace during the electrolysis were performed with an Agilent Technologies 7820A GC system equipped with a thermal conductivity detector. CO and H₂ production was quantitatively detected using a CP-CarboPlot P7 capillary column (27.46 m in length and 25 μm internal diameter). Temperature was held at 150° C. for the detector and 34° C. for the oven. The carrier gas was argon flowing at 9.5 mL/min at constant pressure of 0.4 bars. Injection was performed via a 250-μL gas-tight (Hamilton) syringe previously degassed with CO₂. Conditions allowed detection of both H₂, O₂, N₂, CO, and CO₂. Calibration curves for H₂ and CO were determined separately by injecting known quantities of pure gas.

XPS Analysis

An X-Ray Photoelectron Spectrometer THERMO-VG ESCALAB 250 (RX source K Al (1486.6 eV)) was used.

XAS Data Collection and Analysis

X-ray absorption spectra (XAS) were collected at the LUCIA beamline of SOLEIL with a ring energy of 2.75 GeV and a current of 490 mA. The energy was monochromatized by means of a Si(111) double crystal monochromator. Data were collected in a primary vacuum chamber as fluorescence spectra with an outgoing angle of 5° using a Bruker silicon drift detector. The data were normalized to the intensity of the incoming incident energy and processed with the Athena software from the IFEFFIT package. For the EXAFS analysis, an E₀ value of 7722.0 eV was used for the cobalt K-edge jump energy.

SEM Analysis

Scanning electron microscopy using a field emission gun (SEM-FEG) was performed using a Zeiss Supra 40.

Third Embodiment

The inventors tested the cobalt quarter pyridine (Co(qpy)) in the same cell as the first embodiment. Two types of experiments have been performed on the Co(qpy). The faradaic efficiency for CO has been measured chronopotentiometry at several current densities and the stability of the catalyst has been determined at 50 mA cm⁻².

During chronopotentiometry experiment the Co(qpy) showed faradaic efficiencies for CO higher than 90% at current densities under 100 mA cm⁻². Then, at higher current densities, the faradaic efficiency for CO decreases drastically.

TABLE 4
Chronopotentiometry experiment with Co(qpy)
Cell potential (V)	j/mA · cm−2	% CO
1.71	25	96.6
1.80	50	98.7
1.88	75	98.8
2.24	100	91.6
2.60	125	86.1
2.71	150	64.6
2.73	175	34.7
2.74	200	16.6

In FIG. 26, Co(qpy) can maintain at 50 mAcm⁻² a faradaic efficiency higher than 90% for CO for 12 hours. The decrease is steady until 24 hours of experiments. Then, the faradaic efficiency drops under 40% for CO.

Inventors also tested influence of the electrolyte (cation) used in the flow cell electrolyzer. Results are shown in the Table 5 below.

TABLE 5
Influence of the electrolyte
		CO selectivity	E (V vs	Energy Efficiency
Catalyst	Cation	(%)	RHE)	(%)
CoPc	Na	88.2	−1.10	29
CoPc	Cs	92.3	−1.00	33
Co(qpy)	Na	97.8	−1.01	33
Co(qpy)	Cs	98.7	−0.90	35
FeTNT	Na	98.3	−1.14	33
FeTNT	K	98.6	−0.95	36
FeTNT	Cs	98.9	−0.75	41

REFERENCES

• 1. Azcarate, I., Costentin, C., & al. Through-space charge interaction substituent effects in molecular catalysis leading to the design of the most efficient catalyst of 002-to-CO electrochemical conversion. J. Am. Chem. Soc. 138, 16639-16644 (2016).
• 2. Francke, R., Schille, B., & al. Homogeneously catalyzed electroreduction of carbon dioxide-Methods, mechanisms, and catalysts. Chem. Rev. 116, 4631-4701 (2018).
• 3. Costentin, C., Robert, M., Savéant, J.-M. Catalysis of the electrochemical reduction of carbon dioxide. Chem. Soc. Rev. 42, 2423-2436 (2013).
• 4. Qiao, J., Liu, Y., & al. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 43, 631-675 (2014).
• 5. Elgrishi, N., Chambers, M. B., & al. Molecular polypyridine-based metal complexes as catalysts for the reduction of CO₂. Chem. Soc. Rev. 46, 761-796 (2017).
• 6. Grice, K. A. Carbon dioxide reduction with homogenous early transition metal complexes: Opportunities and challenges for developing CO₂ catalysis. Coord. Chem. Rev. 336, 78-95 (2017).
• 7. Grills, D. C., Ertem, M. Z., & al. Mechanistic aspects of CO₂ reduction catalysis with manganese-based molecular catalysts. Coord. Chem. Rev. 374, 173-217 (2018).
• 8. Loewen, N. D., Neelakantan, T. V., & al. Renewable formate from C—H bond formation with CO₂: using iron carbonyl clusters as electrocatalysts. Acc. Chem. Res. 50, 2362-2370 (2017).
• 9. Takeda, H., Cometto, C., & al. Electrons, photons, protons and earth abundant metal complexes for molecular catalysis of CO₂ reduction. ACS Catal. 7, 70-88 (2017).
• 10. Wang, M., Chen, L., Lau, T-C., Robert, M. Hybrid Co quaterpyridine complex/carbon nanotube catalytic material for CO₂ reduction in water. Angew. Chem. Int. Ed. 57, 7769-7773 (2018).
• 11. Xu, L., Wu, Y., & al. High-Performance Electrochemical CO₂ Reduction Cells Based on Non-noble Metal Catalysts. ACS Energy Lett. 3, 2527-2532 (2018).
• 12. Kutz, R. B., Chen, Q., et al., I. R. Sustainion imidazolium-functionalized polymers for carbon dioxide electrolysis. Energy Technol. 5, 929-936 (2017).
• 13. Dinh, C-T., Garcia de Arguer, F. P., & al. H. High Rate, Selective, and Stable Electroreduction of CO₂ to CO in Basic and Neutral Media. ACS Energy Lett. 3, 2835-2840 (2018).
• 14. Verma, S., Hamasaki, Y., & al. Insights into the low overpotential electroreduction of CO₂ to CO on a supported gold catalyst in an alkaline flow electrolyzer. ACS Energy Lett. 3, 193-198 (2018).
• 15. Zhang, X., Wu, Z., & al., Highly selective and active CO₂ reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 8, 14675 (2017).
• 16. Han, N., Wang, Y., Ma, L. et al., Supported cobalt phthalocyanine for high-performance electrocatalytic CO₂ reduction. Chem 3, 652-664 (2017).
• 17. Li, N., Lu, W., Pei K., Chen, W. Interfacial peroxidase-like catalytic activity of surface-immobilized cobalt phthalocyanine on multiwall carbon nanotubes RSC Advances, 5, 9374-9380 (2015).
• 18. Wang M., Chen L. G., Lau T.-C., and Robert M. A Hybrid Co Quaterpyridine Complex/Carbon Nanotube Catalytic Material for CO₂ Reduction in Water, Angew. Chem. 130, 7895-7899, (2018).

Claims

1. A flow cell electrolyzer to electrochemically reduce CO2 in a CO2-containing reagent gas, passing onto or through a gas diffusion electrode (GDE), into gaseous CO, the flow cell electrolyzer comprising: an anodic compartment comprising: an anode with a current collector,an anodic electrolyte solution, at a controlled flow rate Qa, comprising: a first solvent, and an anodic electrolyte, the first solvent being water,an anodic electrolyte solution inlet and an anodic electrolyte solution outlet connected to the anodic compartment, adapted to circulate the anodic electrolyte solution;a cathodic compartment comprising: a cathodic electrolyte solution, at a controlled flow rate Qc, comprising: a second solvent, and a cathodic electrolyte, the second solvent being H2O,a cathodic electrolyte solution inlet and a cathodic electrolyte solution outlet connected to the cathodic compartment, adapted to circulate the cathodic electrolyte solution, as well as the CO2-containing reagent gas and CO product gas,a gas diffusion electrode comprising, on an electrochemically inert gas diffusion porous current collector having a surface S, a molecular catalyst to electrochemically reduce the CO2 in the CO2-containing reagent gas into said CO product gas in the cathodic electrolyte solution, with by-production of gaseous H2;the molecular catalyst being selected from the group consisting of: metal tetra phenyl porphyrin substituted with at least one +N(C1-C4 alkyl)3 group and having other groups independently selected from the groups consisting of H, OH, F, C(CH3)3, wherein the metal is chosen from among: iron and cobalt,metal phthalocyanine, with the metal chosen among: iron and cobalt,metal phthalocyanine, substituted with at least one group among: +N(C1-C4 alkyl)3, F, C(CH3)3 wherein the metal is chosen among: iron and cobalt, andcobalt quarter pyridine;an anion exchange membrane, impermeable at least to CO2, CO and H2, between the anodic compartment and the cathodic compartment;a channel for passing flow of the CO2-containing reagent gas, at a controlled flow rate Qg, through the porous current collector surface S of the gas diffusion electrode of the cathodic compartment on which there is the molecular catalyst, while the cathodic electrolyte solution circulates in between the gas diffusion electrode and the anion exchange membrane;pumping means adapted to: circulate by pumping the anodic electrolyte solution in the anodic compartment and the cathodic electrolyte solution in the cathodic compartment between the respective inlets and outlets thereof,control flow by pumping the CO2-containing reagent gas in the channel, passing through the porous current collector surface of the gas diffusion electrode,the pumping means being configured to control all flow rates of the cathodic and anodic electrolyte solutions as well as the CO2-containing reagent gas passing through the porous current collector surface S of the gas diffusion electrode;a power supply providing energy necessary to trigger the electrochemical reactions involving the CO2 reagent gas.

2. The flow cell electrolyzer according to claim 1, wherein the anodic and/or cathodic electrolyte solution has a neutral or basic pH.

3. The flow cell electrolyzer according to claim 1, wherein the anodic electrolyte solution and/or the cathodic electrolyte solution has a pH from 9 to 14.

4. (canceled)

5. The flow cell electrolyzer according to claim 1, wherein the CO2-containing reagent gas flow is at atmospheric pressure.

6. The flow cell electrolyzer according to claim 1, wherein the anodic and the cathodic electrolyte solutions are at ambient temperature.

7. The flow cell electrolyzer according to claim 1, wherein the molecular catalyst is a tetra-phenyl iron porphyrin with the formula:

8. The flow cell electrolyzer according to claim 7, wherein: the others of groups among R1 to R10 and R1′ to R10′ are H, orthe others of groups among R1 to R10 and R1′ to R10′ are independently selected from the groups H and F.

9. The flow cell electrolyzer according to claim 7, comprising +N(C1-C4 alkyl)3 groups in the para or ortho position.

10. The flow cell electrolyzer according to claim 1, wherein the molecular catalyst presents the formula:

11. The flow cell electrolyzer according to claim 10, wherein R1 to R16 are H.

12. The flow cell electrolyzer according to any claim 10, at least 1 and at most 8 groups among R1 to R16 being independently +N(C1-C4 alkyl)3.

13. The flow cell electrolyzer according to claim 12, wherein at least one or several of the specific groups R1, R4, R5, R8, R9, R12, R13 and R16 groups, comprises a +N(C1-C4 alkyl)3 substituent.

14. The flow cell electrolyzer according to claim 1, wherein the cathodic electrolyte solution comprises a phosphate buffer or potassium hydroxide, and the anodic electrolyte solution comprises a phosphate buffer or potassium hydroxide.

15. The flow cell electrolyzer according to claim 1, wherein the cathodic electrolyte solution comprises sodium hydroxide or cesium hydroxide and/or the anodic electrolyte solution comprises sodium hydroxide or cesium hydroxide.

16. The flow cell electrolyzer according to claim 1, wherein the molecular catalyst is tetra-phenyl iron porphyrin, wherein: the pH of the anodic electrolyte solution and/or the cathodic electrolyte solution is between from 11.5 to 14,the CO2-containing reagent gas flow passes at atmospheric pressure through the porous current collector surface S of the gas diffusion electrode, andthe anodic and the cathodic electrolyte solutions are at ambient temperature.

17. The flow cell electrolyzer according to claim 10, wherein: the pH of the anodic electrolyte solution and/or the cathodic electrolyte solution is between from 11.5 to 14,the CO2-containing reagent gas flow passes at atmospheric pressure through the porous current collector surface S of the gas diffusion electrode, andthe anodic and the cathodic electrolyte solutions are at ambient temperature.

18. The flow cell electrolyzer according to claim 10, wherein R1 to R16 comprise at least one +N(C1-C4 alkyl)3 group, wherein: the pH of the anodic electrolyte solution and/or the cathodic electrolyte solution is between from 11.5 to 14,the CO2-containing reagent gas flow passes at atmospheric pressure through the porous current collector surface S of the gas diffusion electrode (GDE), andthe anodic and the cathodic electrolyte solutions are at ambient temperature.

19. The flow cell electrolyzer according to claim 1, wherein the molecular catalyst is cobalt quarter pyridine, wherein: the pH of the anodic electrolyte solution and/or the cathodic electrolyte solution is between from 11.5 to 14,the CO2-containing reagent gas flow passes at atmospheric pressure through the porous current collector surface S of the gas diffusion electrode, andthe anodic and the cathodic electrolyte solutions are at ambient temperature.

20. The flow cell electrolyzer according to claim 1, wherein the gas diffusion electrode in the cathodic compartment comprises, on the current collector, an electrode film which contains polymers with the molecular catalysts and wherein the electrode film is deposited or grafted on the current collector.

21. The flow cell electrolyzer according to claim 1, wherein pumping means are configured to recirculate the anodic electrolyte solution and the cathodic electrolyte solution.

22-31. (canceled)