METHOD FOR PREPARING A CATALYST MEDIATING H2 EVOLUTION, SAID CATALYST AND USES THEREOF

• US 20150090604A1
• Filed: 04/04/2013
• Published: 04/02/2015
• Est. Priority Date: 04/05/2012
• Status: Active Grant

• Current Assignee: Commissariat a L'Energie Atomique (AES Corporation), Universite Joseph Fourier
• Original Assignee: Commissariat a L'Energie Atomique (AES Corporation), Freie Universitaet Berlin
• Inventors: Artero, Vincent, Fontecave, Marc, Jacques, Pierre-Andre, Cobo, Saioa, Dau, Holger, Heikamp, Johathan
• Granted Patent: US 10,137,435 B2
• Time in Patent Office: Days
• US Class Current: 205/638
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 2531/0244 Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
• CPC Class Codes: B01J 2531/0247 Tripodal ligands, e.g. comprising the tris(pyrazolyl)borate skeleton, "tpz", neutral analogues thereof by CH/BH exchange or anionic analogues of the latter by exchange of one of the pyrazolyl groups for an anionic complexing group such as carboxylate or -R-Cp
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 2531/847 Nickel
• CPC Class Codes: B01J 2540/10 Non-coordinating groups comprising only oxygen beside carbon or hydrogen
• CPC Class Codes: B01J 31/16 containing coordination complexes
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/182 comprising aliphatic or saturated rings
• CPC Class Codes: B01J 31/1835 comprising aliphatic or saturated rings
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 37/16 Reducing
• CPC Class Codes: B01J 37/345 of ultraviolet wave energy
• CPC Class Codes: B01J 37/348 Electrochemical processes, e.g. electrochemical deposition or anodisation
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C25B 1/02 Hydrogen or oxygen
• CPC Class Codes: C25B 11/073 characterised by the electrocatalyst material
• CPC Class Codes: C25B 11/091 consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
• CPC Class Codes: C25D 3/12 : of nickel or cobalt
• CPC Class Codes: C25D 5/011 : Electroplating using electromagnetic wave irradiation using locally applied electromagnetic radiation C25D5/024
• CPC Class Codes: C25D 7/12 : Semiconductors
• CPC Class Codes: C25D 9/08 : by cathodic processes
• CPC Class Codes: C25D 9/10 : on iron or steel
• CPC Class Codes: C25D 9/12 : on light metals
• CPC Class Codes: H01M 4/8657 : layered
• CPC Class Codes: H01M 4/9016 : Oxides, hydroxides or oxygenated metallic salts
• CPC Class Codes: H01M 4/9041 : Metals or alloys H01M4/92 takes precedence
• CPC Class Codes: H01M 4/9075 : Catalytic material supported on carriers, e.g. powder carriers H01M4/8807, H01M4/881, H01M4/8814, H01M4/925 take precedence
• CPC Class Codes: H01M 4/9083 : on carbon or graphite
• CPC Class Codes: Y02E 60/36 : Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 20/133 : Renewable energy sources, e.g. sunlight

Abstract

The present invention concerns a method for the preparation of a catalyst onto a solid support of a (semi-)conductive material consisting in depositing said catalyst onto said support from a near-neutral aqueous solution containing at least one nickel or cobalt organic complex and at least one basic oxoanion, by a method selected in the group consisting of reductive electrodeposition, photochemical electrodeposition and photoelectrochemical deposition. The present invention also concerns said catalyst and uses thereof.

Claims

1-12. -12. (canceled)

13. A method for the preparation of a catalyst onto a solid support of a conductive or semiconductive material, the method comprising:

depositing said catalyst onto said solid support from a near-neutral aqueous solution containing at least one nickel or cobalt organic complex and at least one basic oxoanion, using a method selected from the group consisting of reductive electrodeposition, photochemical electrodeposition, and photoelectrochemical deposition.

14. The method according to claim 13, wherein the conductive or semiconductive material of said solid support is selected from the group consisting of a metallic material, a carbon material, a semiconductor or conductor metal oxide, nitride, and chalcogenide.

15. The method according to claim 13, wherein the conductive or semiconductive material of said solid support is selected from the group consisting of silicon, brass, stainless steel, iron, copper, nickel, cobalt, aluminium, silver, gold, titanium, carbon black, single or multi-walled carbon nanotubes (CNT), fullerenic nanoparticles, graphite, glassy carbon, graphene, reduced graphene oxide, doped diamond, TiO₂, NiO, ZnO, ZrO₂, ITO, SnO₂, WO₃, Fe₂O₃, BiVO₄, Ta₂O₅, Ta₃N₅, TaON, ZnS, ZnSe, CdS, CdSe, CdTe, ZnTe, and composites of these materials, possibly doped with other elements.

16. The method according to claim 13, wherein the near-neutral aqueous solution has a pH of between 5 and 9.

17. The method according to claim 13, wherein the near-neutral aqueous solution has a pH of between 6 and 8.

18. The method according to claim 13, wherein the near-neutral aqueous solution has a pH of between 6.3 and 7.7.

19. The method according to claim 13, wherein the near-neutral aqueous solution has a pH of between 6.5 and 7.5.

20. The method according to claim 13, wherein the near-neutral aqueous solution has a pH of between 6.7 and 7.3.

21. The method according to claim 13, wherein the near-neutral solution is an aqueous solution having a pH of 7.

22. The method according to claim 13, wherein said cobalt or nickel organic complex is selected from the group consisting of cobalt or nickel dioxime/diimine complex;

and cobalt or nickel amine/imine/pyridine complex.

23. The method according to claim 13, wherein said cobalt or nickel organic complex is selected from the group consisting of [Co(DO)(DOH)pnCl₂] with (DOH)(DOH)pn representing N²,N²′

-propanediylbis(2,3-butandione 2-imine 3-oxime);

[Co(DO)(DOH)pnBr₂];

[Co((DO)₂BF₂)pnBr₂] with ((DO)₂BF₂)pn representing N²,N²′

-propanediylbis(2,3-butandione 2-imine 3-oximato)-N¹,N^1′

-difluoroboryl;

[Co(MO)(MOH)pnCl₂] with (MOH)(MOH)pn representing N²,N²′

-propanediylbis(1,2-propandione 2-imine 1-oxime);

[Ni((DO)₂BF₂)pn](ClO₄);

[Co(dmgBF₂)₂(H₂O)₂] with dmgH₂ representing dimethylglyoxime;

[Co(dmgH)₂pyCl];

[Co(dmgH)₂(OH₂)₂];

[Co(dmgBF₂)₂(DMF)₂];

[Co(dmgBF₂)₂(CH₃CN)₂];

[Co(dpgBF₂)₂(H₂O)₂] with dpgH₂ representing diphenylglyoxime;

[Co(dpgBF₂)₂(DMF)₂];

[Co(dpgBF₂)₂(CH₃CN)₂];

[Ni(dmgBF₂)₂];

[Ni(dmgH)₂][Ni(DO)(DOH)pn](ClO₄);

[Ni(MO)(MOH)pnCl];

[Ni((DO)₂BF₂)pn](ClO₄);

[Co(DO)(DOH)pnBr(PPh₃)];

[Co(DO)(DOH)pn(PPh₃)];

[Co(dmg)₃(BF)₂]⁺;

[Co(dpg)₃(BF)₂]⁺;

[Co(dmg)₃(BPh)₂]^0/1+ and [Co(dpg)₃(BPh)₂]^0/1+.

24. The method according to claim 13, wherein said basic oxoanion is selected from the group consisting of a phosphate, carbonate, arsenate, borate, vanadate, chromate, phosphonate, phosphite, nitrate, nitrite, sulphate, sulphonate, molybdate, and tungstate.

25. The method according to claim 13, wherein the reductive electrodeposition comprises applying to said solid support a potential below −

0.4 V versus Ag/AgCl.

26. The method according to claim 13, wherein the reductive electrodeposition comprises applying to said solid support a potential below −

0.6 V versus Ag/AgCl.

27. The method according to claim 13, wherein the reductive electrodeposition comprises applying to said solid support a potential below −

0.8 V versus Ag/AgCl.

28. The method according to claim 13, wherein the reductive electrodeposition comprises applying to said solid support a potential of about −

1 V versus Ag/AgCl.

29. A catalyst obtainable by the preparation method according to claim 13,

wherein said catalyst has a nanoparticulate morphology with nanoparticles having an average diameter of between 5 nm and 150 nm, and consisting of elemental cobalt/nickel covered or coated by a cobalt/nickel oxo/hydroxo-/oxoanion layer or compound.

30. A catalyst obtainable by the preparation method according to claim 13,

wherein said catalyst has a nanoparticulate morphology with nanoparticles having an average diameter of between 10 nm and 100 nm, and consisting of elemental cobalt/nickel covered or coated by a cobalt/nickel oxo/hydroxo-/oxoanion layer or compound.

31. An electrode coated by a catalyst according to claim 29.

32. An electrode obtained by the preparation method according to claim 25.

33. A method for mediating hydrogen evolution comprising implementing a catalyst according to claim 29.

34. A method for mediating hydrogen evolution comprising implementing a catalyst obtained by the preparation method according to claim 32.

35. A method for mediating hydrogen evolution comprising implementing an electrode according to claim 31.

36. A method for mediating hydrogen evolution comprising implementing an electrode according to claim 32.

37. The method according to claim 15, wherein the conductive or semiconductive material is doped with one or more elements other than said selected material.