Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from alcohols

1. A composition comprising a molybdenum dioxo moiety coupled to a support component comprising an oxygen moiety, said composition absent an MoO 3 moiety, the composition having a Mo surface density in the range from 0.10 to 0.22 Mo/nm 2 .

2. The composition of claim 1 wherein said support component comprises a metal oxide.

3. The composition of claim 2 wherein said support component comprises Al 2 O 3 or anatase TiO 2 .

4. The composition of claim 1 wherein said support component comprises oxygen-functionalized multi-walled carbon nanotubes or oxygen-functionalized activated carbon.

5. The composition of claim 1 wherein the composition is the reaction product of MoO 2 Cl 2 (dme) and the support component is selected from oxygen-functionalized activated carbon, Al 2 O 3 , anatase TiO 2 and oxygen-functionalized multi walled carbon nanotubes.

6. The composition of claim 4 wherein the molybdenum dioxo moiety is coupled to the oxygen-functionalized activated carbon, said composition absent chloride.

7. The composition of claim 6 wherein said Mo dioxo moiety comprises up to about 5.0 wt. % of said composition.

8. A method of producing hydrogen and an aldehyde from methanol or ethanol, said method comprising:

providing a reaction medium comprising an alcohol selected from methanol, ethanol and a combination thereof; and

contacting said medium with the composition of claim 1 , said contact for a time and at a temperature sufficient to oxidize said alcohol to said aldehyde and produce hydrogen gas.

9. The method of claim 8 wherein said alcohol is provided as a neat alcohol, an alcohol in an organic solvent, or an aqueous solution of an alcohol.

10. The method of claim 9 wherein said alcohol is provided as an aqueous solution of the alcohol, comprising up to about 90% water.

11. The method of claim 8 wherein said alcohol is provided in toluene.

12. The method of claim 8 wherein said reaction medium is at a temperature less than about 100° C.

13. The method of claim 8 comprising regeneration of said composition, said regeneration by at least one of providing a said alcohol as an aqueous solution and washing said composition after reaction with said alcohol.

14. The method of claim 8 incorporated into a process selected from batch, semi-batch and continuous processes.

15. The method of claim 8 substantially absent production of carbon monoxide or carbon dioxide.

16. A method of producing hydrogen and an aldehyde from methanol or ethanol, said method comprising:

providing a reaction medium comprising an alcohol selected from methanol, ethanol and a combination thereof; and

contacting said medium with the composition of claim 5 , said contact for a time and at a temperature sufficient to oxidize said alcohol to said aldehyde and produce hydrogen gas.

17. A method of producing hydrogen and an aldehyde from methanol or ethanol without production of carbon monoxide or carbon dioxide, said method comprising:

providing a reaction medium comprising a composition comprising water and an alcohol selected from methanol and ethanol and a combination thereof, said composition comprising up to about 90% water; and

contacting said medium with the composition of claim 6 , said contact for a time and at a temperature sufficient to oxidize a said alcohol to a said aldehyde and produce hydrogen gas substantially without production of carbon monoxide or carbon dioxide.

18. The method of claim 17 wherein said reaction medium is at a temperature less than about 100° C.

19. The method of claim 17 comprising regeneration of said composition, said regeneration by at least one of providing a said alcohol as an aqueous solution and washing said composition after reaction with said alcohol.

20. The method of claim 17 incorporated into a process selected from batch, semi-batch and continuous processes.

21. A composition comprising a molybdenum dioxo moiety coupled to a support component comprising an oxygen moiety, said composition absent an MoO 3 moiety, wherein said support component comprises oxygen-functionalized activated carbon, wherein said composition is absent chloride, and wherein the density of said Mo dioxo moiety on said oxygen-functionalized activated carbon is up to about 0.22 Mo/nm 2 .

22. The composition of claim 21 wherein said Mo dioxo moiety comprises up to about 2.5 wt. % of said composition.

23. The composition of claim 22 wherein said Mo dioxo moiety comprises about 2.1 wt. % of said composition.

24. The composition of claim 23 wherein the density of said Mo dioxo moiety on said activated carbon is about 0.10 Mo/nm 2 .