Ruthenium or osmium complexes and their uses as catalysts for water oxidation
The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.
1. A complex having the structure of formula (I):
wherein M is ruthenium (Ru) or osmium (Os), L 2 is a tridentate ligand,
L 3 is a monodentate ligand, n is 2 or 1, and
L 1 is a bidentate ligand selected from the group consisting of
2. A complex having the structure of formula (I):
wherein M is ruthenium (Ru) or osmium (Os), L 1 is a bidentate ligand,
L 2 is a tridentate ligand, n is 2 or 1, and
L 3 is OH 2 .
3. A complex comprising Formula A or B:
wherein, for Formula A and B, the ligand
is independently selected from the group consisting of
4. A complex comprising a structure selected from the group consisting of [Ru(tpy)(bpy)(OH 2 )] 2+ , [Ru(tpy)(bpm)(OH 2 )] 2+ , [Ru(tpy)(bpz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-py)(OH 2 )] 2+ , [Ru(DMAP)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-py)(OH 2 )] 2+ , {Ru(Mebimpy)[4,4′-((HO) 2 OPCH 2 ) 2 bpy](OH 2 )} 2+ and Os(tpy)(bpy)(OH 2 ) 2+ .
5. A catalyst comprising a complex having a structure selected from the group consisting of [Ru(tpy)(bpy)(OH 2 )] 2+ , [Ru(tpy)(bpm)(OH 2 )] 2+ , [Ru(tpy)(bpz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-py)(OH 2 )] 2+ , [Ru(DMAP)(bpy)(OH 2 )] 2+ , [Ru (Mebimpy)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-py)(OH 2 )] 2+ , {Ru(Mebimpy)[4,4′-((HO) 2 OPCH 2 ) 2 bpy](OH 2 )} 2+ and Os(tpy)(bpy)(OH 2 ) 2+ .
6. An electrode comprising (a) a complex according formula (I):
wherein M is ruthenium (Ru) or osmium (Os), L 1 is a bidentate ligand, L 2 is a tridentate ligand, L 3 is a monodentate ligand, and n is 2 or 1, and (b) a supporting substrate on which said catalyst is supported.
7. The electrode of claim 6 , wherein the (a) complex has a structure selected from the group consisting of [Ru(tpy)(bpy)(OH 2 )] 2+ , [Ru(tpy)(bpm)(OH 2 )] 2+ , [Ru(tpy)(bpz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-py)(OH 2 )] 2+ , [Ru(DMAP)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-py)(OH 2 )] 2+ , {Ru(Mebimpy)[4,4′-((HO) 2 OPCH 2 ) 2 bpy](OH 2 )} 2+ and Os(tpy)(bpy)(OH 2 ) 2+ .
8. The electrode of claim 6 , wherein (b) the supporting substrate comprises fluorine-doped SnO 2 (FTO) or Sn(IV)-doped In 2 O 3 (ITO).
9. A photo-electrochemical cell comprising a catalyst comprising a complex, wherein the complex has a structure selected from the group consisting of [Ru(tpy)(bpy)(OH 2 )] 2+ , [Ru(tpy)(bpm)(OH 2 )] 2+ , [Ru(tpy)(bpz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-py)(OH 2 )] 2+ , [Ru(DMAP)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-py)(OH 2 )] 2+ , {Ru(Mebimpy)[4,4′-((HO) 2 OPCH 2 ) 2 bpy](OH 2 )} 2+ and Os(tpy)(bpy)(OH 2 ) 2+ .
10. A photoelectrolytic device comprising (a) a catalyst comprising a complex according to formula (I):
wherein M is ruthenium (Ru) or osmium (Os), L 1 is a bidentate ligand, L 2 is a tridentate ligand, L 3 is a monodentate ligand, and n is 2 or 1, and (b) a supporting substrate on which said catalyst is supported.
11. The device of claim 10 , wherein the complex has a structure selected from the group consisting of [Ru(tpy)(bpy)(OH 2 )] 2+ , [Ru(tpy)(bpm)(OH 2 )] 2+ , [Ru(tpy)(bpz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(tpy)(Mebim-py)(OH 2 )] 2+ , [Ru(DMAP)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(bpy)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-pz)(OH 2 )] 2+ , [Ru(Mebimpy)(Mebim-py)(OH 2 )] 2+ , {Ru(Mebimpy)[4,4′-((HO) 2 OPCH 2 ) 2 bpy](OH 2 )} 2+ and Os(tpy)(bpy)(OH 2 ) 2+ .
12. The device of claim 10 , further comprising a proton acceptor base.
13. The device of claim 10 , wherein the proton acceptor base is selected from the group consisting of H 2 PO 4 − acetate (OAc − ), and HPO 4 2− .
14. The complex of claim 4 , wherein the complex comprises the structure {Ru(Mebimpy)[4,4′-((HO) 2 OPCH 2 ) 2 bpy](OH 2 )} 2+ .