Filter-press photoelectrochemical water oxidation and co2 reduction cell

Patent metadata

Field	Value
Publication number	US-2018023203-A1
Application number	US-201515537046-A
Country	US
Kind code	A1
Filing date	Dec 18, 2015
Priority date	Dec 19, 2014
Publication date	Jan 25, 2018
Grant date	—

Abstract

The present disclosure relates to methods and devices for use in photoelectrochemical reduction of CO 2 . In particular, it is disclosed a filter-press photoelectrochemical cell for producing a reduction product from CO 2 and a method for the photoelec-trochemical reduction of CO 2 .

First claim

1 . A filter-press photoelectrochemical cell comprising:
a) a cathodic compartment ( 1 ) which comprises a cathode support frame ( 150 ) comprising a cathodic material ( 4 ) which acts as a cathode; a first fluid and gaseous CO 2 distribution frame ( 6 ) and a second fluid and gaseous CO 2 distribution frame ( 7 ); one or more cathodic gaskets ( 81 , 82 , 83 and 84 ) , the cathodic gaskets being placed between the cathode support frame ( 150 ) and the distribution frames ( 6 , 7 ), and as lateral ends of the cathodic compartment; wherein the cathode support frame ( 150 ) is disposed between the first and second distribution frames ( 6 ; 7 ); b) an anodic compartment ( 2 ) which comprises an anode support frame ( 250 ) comprising an anodic material ( 5 ) which acts as an anode; a fluid distribution frame ( 8 ) arranged such that the fluid distribution frame ( 8 ) is on a portion of the anodic compartment closer to the membrane ( 3 ) than the anode support frame ( 250 ); and one or more anodic gaskets ( 85 and 86 ), the anodic gaskets being placed between the anode support frame ( 250 ) and the distribution frame ( 8 ), and as lateral ends of the anodic compartment; and c) an ion-exchange membrane ( 3 ) disposed between the cathodic compartment ( 1 ) and the anodic compartment ( 2 ); wherein
i) the cathodic material ( 4 ) is a conductive porous electrode with immobilized CO 2 electrocatalyst material;
ii) the first and second fluid and gaseous CO 2 distribution frames ( 6 , 7 ) and cathodic gaskets ( 81 , 82 , 83 and 84 ) are arranged such that in use they allow introducing a catholyte and gaseous CO 2 separately into the cathodic compartment ( 1 ) through different inlet ports ( 11 a , 11 b ) and they allow exiting the catholyte, liquid and gaseous products and/or unreacted CO 2 jointly through an outlet port ( 12 );
iii) the fluid distribution frame ( 8 ), the anode support frame ( 250 ) and anodic gaskets ( 85 and 86 ) are arranged in such a way that in use they allow introducing an anolyte into the anodic compartment ( 2 ) through an inlet port ( 13 ), and they allow exiting the anolyte and oxidation products jointly through an outlet port ( 14 );
iv) the anodic material ( 5 ), is a photocatalytic anodic material, and is located in a side facing the membrane ( 3 ) of an optical window ( 15 ) of the anode support frame ( 250 ); and is arranged such that in use is able to be in contact with the anolyte which is introduced into the anodic compartment via the inlet port ( 13 ) and, is able to be activated when the radiation used to irradiate the anodic compartment ( 2 ) reaches the optical window ( 15 ) by its opposite side which is not facing the membrane ( 3 ); and
v) the photocatalytic anodic material ( 5 ) and the gas diffusion cathodic material ( 4 ) have a surface area ratio comprised from 1:1 to 1:0.1.

2 . The filter-press photoelectrochemical cell according to claim 1 , wherein the immobilized CO 2 electrocatalyst material of the cathodic material ( 4 ) is selected from
a) a metal with a high overpotential to hydrogen evolution, low CO adsorption and high overpotential for CO 2 to CO 2 radical ion; selected from the group consisting of Pb, Hg, In, Sn, Cd, Tl and Bi; b) a metal with a medium overpotential to hydrogen evolution and low CO adsorption; selected from the group consisting of Au, Ag, Zn, Pd and Ga; c) a metal with a high CO adsorption and a medium overpotential to hydrogen evolution; selected from the group consisting of Cu; d) a metal with a relatively low overpotential to hydrogen evolution and a high CO adsorption, selected from the group consisting of Ni, Fe, Pt, Ti; e) an oxide of any of the metals of a), b), c) or d) type; and f) combinations thereof;
the material being deposited on a highly porous and conductor support.

3 . The filter-press photoelectrochemical cell according claim 1 , wherein the immobilized CO 2 electrocatalyst material of the cathodic material ( 4 ) is selected from the group consisting of Sn, Pb, Hg, Bi, In, Cd, Tl, Cu, CuO, Cu 2 O, Au, Ag, Zn, Pd, Ga and combinations thereof, the materials deposited on a highly porous and conductor support.

4 . The filter-press photoelectrochemical cell according to claim 1 , wherein the immobilized CO 2 electrocatalyst material of the cathodic material ( 4 ) is selected from the group consisting of Pb, Hg, In, Sn, Cd, Tl, Bi and combinations thereof, the materials deposited on a highly porous and conductor support.

5 . The filter-press photoelectrochemical cell according to claim 1 , wherein the highly porous and conductor support is selected from carbon paper, carbon based nanofibres, metallic meshes, and metal foams.

6 . The filter-press photoelectrochemical cell according to claim 1 , wherein the photocatalytic anodic material ( 5 ) is selected from semiconductor materials with a bandgap between 1.1 and 3.4 eV and valence band edge equal to or higher than 1.23V vs RHE.

7 . The filter-press photoelectrochemical cell according to claim 6 , wherein the photocatalytic anodic material ( 5 ) is selected from the group consisting of TiO 2 , WO 3 , BiVO 4 , Fe 2 O 3 , SrTiO 3 , Si, amorphous Si, GaAs, GaN, MoS 2 , WSe 2 , MoSe 2 and combinations thereof

8 . The filter-press photoelectrochemical cell according to claim 1 , wherein the anolyte comprises
a) at least one polar protic solvent comprising at least one supporting electrolyte, and b) optionally a buffer solution;
the supporting electrolyte is a salt of the formula M m Y r , in which M is selected from lithium, potassium, sodium, magnesium, calcium, and strontium; Y is either a hydroxide ion or a counter ion coming from mineral acids selected from halides, sulfates, nitrates, chlorates or phosphates.

9 . The filter-press photoelectrochemical cell according to claim 8 , wherein the salt included as a supporting electrolyte is selected from NaOH, KOH, H 2 SO 4 , KCl, HCl, H 3 PO 4 , NaHCO3, K 2 HPO 4 , K 2 SO 4 , Na 2 SO 4 .

10 . The filter-press photoelectrochemical cell according to claim 1 , wherein the catholyte comprises
a) at least one polar protic solvent comprising at least one supporting electrolyte, and b) optionally a buffer solution;
the supporting electrolyte is a salt of the formula M m X n in which: M is selected from magnesium, calcium, lithium, potassium and sodium; X is selected from anions of weak or strong acids selected from carbonates, bicarbonates, sulfates, hydroxides and halides.

11 . The filter-press photoelectrochemical cell according to claim 10 , wherein the salt included as a supporting electrolyte is selected from NaHCO 3 , KHCO 3 , K 2 CO 3 , Na 2 SO 4 , K 2 SO 4 , KCl, KClO 4 .

12 . The filter-press photoelectrochemical cell according to claim 1 , wherein the ion-exchange membrane is an ion-exchange membrane that permits selected ions to cross the membrane to balance the process stoichiometry.

13 . The filter-press photoelectrochemical cell according to claim 1 , wherein the ion-exchange membrane is a cation exchange membrane.

14 . A method for reducing carbon dioxide comprising the steps of:
i) providing an filter-press photoelectrochemical cell as defined in claim 1 ; ii) feeding the filter-press photoelectrochemical cell with an anolyte through an inlet port ( 13 ) into the anodic compartment ( 2 ), a catholyte through an inlet port ( 11 a ) into the cathodic compartment ( 1 ) and a gas containing CO 2 through a different inlet port ( 11 b ) into the cathodic compartment ( 1 ); iii) applying to the cell an external electrical potential between cathode ( 4 ) and anode ( 5 ) with bias

Assignees

• Repsol Sa

Inventors

• Hernández Alonso María Dolores
• Penelas Pérez Germán
• ANDREU Tresa
• Irtem Erdem
• Parra Andrés
• Fábrega Cristián
• Morante Juan Ramón

Classifications

• B01J23/38

  of noble metals · CPC title

• C25B1/00

  Electrolytic production of inorganic compounds or non-metals · CPC title

• B01J23/70

  of the iron group metals or copper · CPC title

• C01B32/50

  Carbon dioxide · CPC title

• C25B9/20 Primary

  Chemistry & Metallurgy · mapped topic