Molecular molybdenum persulfide and related catalysts for generating hydrogen from water

Patent metadata

Field	Value
Publication number	US-9315909-B2
Application number	US-201213403573-A
Country	US
Kind code	B2
Filing date	Feb 23, 2012
Priority date	Oct 8, 2009
Publication date	Apr 19, 2016
Grant date	Apr 19, 2016

Abstract

New metal persulfido compositions of matter are described. In one embodiment the metal is molybdenum and the metal persulfido complex mimics the structure and function of the triangular active edge site fragments of MoS 2 , a material that is the current industry standard for petroleum hydro desulfurization, as well as a promising low-cost alternative to platinum for electrocatalytic hydrogen production. This molecular [(PY5W 2 )MoS 2 ] x+ containing catalyst is capable of generating hydrogen from acidic-buffered water or even seawater at very low overpotentials at a turnover frequency rate in excess of 500 moles H 2 per mole catalyst per second, with a turnover number (over a 20 hour period) of at least 19,000,000 moles H 2 per mole of catalyst.

First claim

We claim:

1. An organo metal persulfide complex having the following structural formula:

wherein M is a high oxidation state metal selected from the group comprising Mo, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Tungsten; W, X, Y, and Z are selected from the group comprising hydrogen, methyl, a higher alkyl or aryl group, a halide such as P, Cl, Br, and I, CF3, or SiR3, where substitutions at the X, Y, and Z positions may be optional, and the valance states x + and x− of the ions are integers.

2. The complex of claim 1 wherein both x+ and x− equal 2.

3. The complex of claim 1 wherein the anion is CF 3 SO 3 .

4. The complex of claim 1 wherein the metal is Molybdenum.

5. An organo metal-persulfied complex containg composition of matter comprising:
[(PY5W 2 )MoS 2 ] 2+
wherein PY5W 2 equals (NC 5 XYZ)(NC 5 H 4 ) 4 C 2 W 2 ; and,
W, X, Y, and Z are selected from the group comprising H, methyl, a higher alkyl or aryl group, a halide such as F, Cl, Br,and I, CF3, or SiR3, and where substitutions at the X, Y, and Z positions may be optional.

6. The organo metal-persulfied complex of claim 5 wherein [(PY5Me 2 )Mo(S 2 )](CF 3 SO 3 ) 2 .

Assignees

• Long Jeffrey R
• Chang Christopher J
• Karunadasa Hemamala I
• Majda Marcin
• Univ California

Inventors

• Long Jeffrey R
• Chang Christopher J
• Karunadasa Hemamala I
• Majda Marcin

Classifications

• B01J2531/0241

  Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution · CPC title

• B01J31/226

  Sulfur, e.g. thiocarbamates · CPC title

• B01J2531/62

  Chromium · CPC title

• B01J2531/46

  Titanium · CPC title

• B01J2531/16

  Copper · CPC title