Molecular molybdenum persulfide and related catalysts for generating hydrogen from water

Patent metadata

Field	Value
Publication number	US-2016010219-A1
Application number	US-201514859763-A
Country	US
Kind code	A1
Filing date	Sep 21, 2015
Priority date	Oct 8, 2009
Publication date	Jan 14, 2016
Grant date	—

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 . A method for deriving hydrogen from water comprising:
dissolving an organo metal persulfide complex in a water bath, said water bath containing both an anode and a cathode, and an electrolyte, the water bath further maintained at a low pH, wherein the 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 F, 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;
applying a negative potential to the cathode;
whereby the organo metal persulfide complex picks up electrons at the negative electrode, and thereafter reacts with water to release hydrogen.

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

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

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

5 . The method of claim 1 wherein the water bath is maintained at a pH of less than 5.

6 . The method of claim 1 wherein the water bath is maintained at a pH of less than 4.

7 . The method of claim 1 wherein the water bath is maintained at a pH of about 3.

8 . The method of claim 1 wherein the negative potential applied to the cathode is an overpotential of approximately −400 mV compared to the standard hydrogen electrode.

Assignees

• Univ California

Inventors

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

Classifications

• B01J31/226

  Sulfur, e.g. thiocarbamates · CPC title

• C25B1/04 Primary

  by electrolysis of water · CPC title

• B01J31/1815

  with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine · CPC title

• B01J2531/64

  Molybdenum · CPC title

• C25B3/25 Primary

  Reduction · CPC title