Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof

Patent metadata

Field	Value
Publication number	US-10137435-B2
Application number	US-201314390550-A
Country	US
Kind code	B2
Filing date	Apr 4, 2013
Priority date	Apr 5, 2012
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

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.

First claim

The invention claimed is:

1. 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,
wherein the catalyst consists of elemental cobalt/nickel covered or coated by a cobalt/nickel oxo/hydroxo-oxoanion layer.

2. The method according to claim 1 , 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.

3. The method according to claim 1 , 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, TiO 2 , NiO, ZnO, ZrO 2 , ITO, SnO 2 , WO 3 , Fe 2 O 3 , BiVO 4 , Ta 2 O 5 , Ta 3 N 5 , TaON, ZnS, ZnSe, CdS, CdSe, CdTe, ZnTe, and composites of these materials, possibly doped with other elements.

4. The method according to claim 1 , wherein the near-neutral aqueous solution has a pH of between 5 and 9.

5. The method according to claim 1 , wherein the near-neutral aqueous solution has a pH of between 6 and 8.

6. The method according to claim 1 , wherein the near-neutral aqueous solution has a pH of between 6.3 and 7.7.

7. The method according to claim 1 , wherein the near-neutral aqueous solution has a pH of between 6.5 and 7.5.

8. The method according to claim 1 , wherein the near-neutral aqueous solution has a pH of between 6.7 and 7.3.

9. The method according to claim 1 , wherein the near-neutral solution is an aqueous solution having a pH of 7.

10. The method according to claim 1 , 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.

11. The method according to claim 1 , wherein said cobalt or nickel organic complex is selected from the group consisting of [Co(DO)(DOH)pnCl 2 ] with (DOH)(DOH)pn representing N 2 ,N 2 ′-propanediylbis(2,3-butandione 2-imine 3-oxime); [Co(DO)(DOH)pnBr 2 ]; [Co((DO) 2 BF 2 )pnBr 2 ] with ((DO) 2 BF 2 )pn representing N 2 ,N 2 ′-propanediylbis(2,3-butandione 2-imine 3-oximato)-N 1 ,N 1′ -difluoroboryl [Co(MO)(MOH)pnCl 2 ] with (MOH)(MOH)pn representing N 2 ,N 2 ′-propanediylbis(1,2-propandione 2-imine 1-oxime); [Ni((CO) 2 BF 2 )pn](ClO 4 ); [Co(dmgBF 2 ) 2 (H 2 O) 2 ] with dmgH 2 representing dimethylglyoxime; [Co(dmgH) 2 pyCl]; [Co(dmgH) 2 (OH 2 ) 2 ]; [Co(dmgBF 2 ) 2 (DMF) 2 ]; [Co(dmgBF 2 ) 2 (CH 3 CN) 2 ]; [Co(dpgBF 2 ) 2 (H 2 O) 2 ] with dpgH 2 representing diphenylglyoxime; [Co(dpgBF 2 ) 2 (DMF) 2 ]; [Co(dpgBF 2 ) 2 (CH 3 CN) 2 ]; [Ni(dmgBF 2 ) 2 ]; [Ni(dmgH) 2 ] [Ni(DO)(DOH)pn](ClO 4 ); [Ni(MO)(MOH)pnCl]; [Ni((DO) 2 BF 2 )pn](ClO 4 ); [Co(DO)(DOH)pnBr(PPh 3 )]; [Co(DO)(DOH)pn(PPh 3 )]; [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+ .

12. The method according to claim 1 , 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.

13. The method according to claim 1 , wherein the reductive electrodeposition comprises applying to said solid support a potential below −0.4 V versus Ag/AgCl.

14. The method according to claim 1 , wherein the reductive electrodeposition comprises applying to said solid support a potential below −0.6 V versus Ag/AgCl.

15. The method according to claim 1 , wherein the reductive electrodeposition comprises applying to said solid support a potential below −0.8 V versus Ag/AgCl.

16. The method according to claim 1 , wherein the reductive electrodeposition comprises applying to said solid support a potential of about −1 V versus Ag/AgCl.

17. A method for mediating hydrogen evolution comprising implementing the catalyst obtained by the preparation method according to claim 1 .

18. The method according to claim 3 , wherein the conductive or semiconductive material is doped with one or n ore elements other than said selected material.

Assignees

• Commissariat Energie Atomique
• Univ Berlin Freie
• Univ Joseph Fourier

Inventors

• Artero Vincent
• Fontecave Marc
• Cobo Saioa
• Jacques Pierre-Andre
• Dau Holger
• Heidkamp Jonathan

Classifications

• H01M4/9083

  on carbon or graphite · CPC title

• H01M4/8657

  layered · CPC title

• B01J2531/0244

  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 title

• B01J37/16

  Reducing · CPC title

• B01J23/75 Primary

  Cobalt · CPC title