Non-platinum group metal electrocatalysts using metal organic framework materials and method of preparation

• US 8,835,343 B2
• Filed: 09/27/2010
• Issued: 09/16/2014
• Est. Priority Date: 09/27/2010
• Status: Active Grant

• Current Assignee: UChicago Argonne LLC
• Original Assignee: UChicago Argonne LLC
• Inventors: Liu, Di-Jia, Ma, Shengqian, Goenaga, Gabriel A.
• Primary Examiner(s): Li, Jun
• Application Number:
  US12/891,509
• Publication Number:
  US 20120077667A1
• Time in Patent Office: 1,450 Days
• Field of Search: 502/101, 502/165, 502/167, 502/200, 502/324, 502/326
• US Class Current: 502/101
• CPC Class Codes: B01J 31/1691 Coordination polymers, e.g. metal-organic frameworks [MOF] preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F
• CPC Class Codes: B01J 31/18 containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: H01M 2008/1095 Fuel cells with polymeric electrolytes
• CPC Class Codes: H01M 2250/20 Fuel cells in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 4/8605 Porous electrodes
• CPC Class Codes: H01M 4/8875 Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
• CPC Class Codes: H01M 4/8882 Heat treatment, e.g. drying, baking
• CPC Class Codes: H01M 4/9008 Organic or organo-metallic compounds
• CPC Class Codes: H01M 4/9041 Metals or alloys H01M4/92 takes precedence
• CPC Class Codes: H01M 8/10 Fuel cells with solid electrolytes
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02T 90/40 Application of hydrogen technology to transportation, e.g. using fuel cells

Abstract

A method of preparing a nitrogen containing electrode catalyst by converting a high surface area metal-organic framework (MOF) material free of platinum group metals that includes a transition metal, an organic ligand, and an organic solvent via a high temperature thermal treatment to form catalytic active sites in the MOF. At least a portion of the contained organic solvent may be replaced with a nitrogen containing organic solvent or an organometallic compound or a transition metal salt to enhance catalytic performance. The electrode catalysts may be used in various electrochemical systems, including a proton exchange membrane fuel cell.

Claims

1. A method of preparing a high surface area electrode catalyst free of platinum group metals (PGM) for use in a fuel cell, comprising:

preparing a metal-organic framework (MOF) material consisting of a plurality of pores and also a non-PGM first transition metal catalytic center chemically bonded via a metal-nitrogen containing bond to an organic multidentate ligand in of the MOF material, the organic multidentate ligand and a first organic solvent contained within a portion of the plurality of pores, comprising;

dissolving a first transition metal salt in the first organic solvent to form a metal salt solution, wherein the non-PGM transition metal in the transition metal salt is selected from the group consisting of;

Co, Fe, Ni, Cr, Cu, Mn, Ta and W;

dissolving the organic multidentate ligand in the first organic solvent to form a ligand solution;

mixing a predetermined molar ratio of the metal salt solution and the ligand solution wherein the multidentate ligand is selected from the group consisting of imidazolate, pyrazolate, piperazine, tetrazolate, and combinations thereof into a reaction mixture; and

forming the MOF material by the step consisting of chemically bonding the non-PGM transition metal to the organic multidentate ligand to form the MOF material through a chemical reaction of forming a metal-nitrogen containing bond to the organic multidentate ligand and then separating the MOF material from the reaction mixture;

substituting at least a portion of the contained first organic solvent with a second chemical moiety to enhance formation of electrocatalytic active sites in the MOF material; and

thermally treating the MOF material for a predetermined period within an environment at a thermal conversion temperature to form the high surface area electrode catalyst having a plurality of uniformly distributed electrocatalytic active sites with catalytic centers arising from the non-PGM first transition metal chemically bonded in the thermally converted MOF material.

2. The method of claim 1, wherein the transition metal salt is selected from the group consisting of:

a nitrate, an acetate, and a chloride of the transition metal.

3. The method of claim 1, wherein the second chemical moiety is dimensioned to infiltrate the plurality of pores and form a plurality of bimetallic electrocatalytic active sites, and wherein the second chemical moiety is one of an organometallic complex and a second metal salt.

4. The method of claim 1, wherein the first organic solvent is selected from the group consisting of:

dimethylformamide (DMF), diethyformamide (DEF), dimethylacetamide (DMA), cynamide, and pyridine.

5. The method of claim 3, wherein the organometallic complex is selected from the group consisting of:

ferrocene, cobaltocene, and Prussian blue; and

wherein the second metal salt is selected from the group consisting of;

a metal nitrate, a metal acetate, and a metal chloride.

6. The method of claim 1 further comprising dissolving at least one templating agent containing nitrogen with the first organic solvent to form the ligand solution.

7. The method of claim 1, wherein the predetermined period is between about 60 minutes and about 90 minutes, and wherein the thermal conversion temperature is between about 700°

C. to about 800°

C.

8. The method of claim 7, wherein the environment comprises one of an inert carrier gas and a reductive carrier gas, wherein the inert carrier gas is selected from the group consisting Ar, He and N₂, and wherein the reductive carrier gas is selected from the group consisting of:

NH₃, pyridine, and acetonitrile.

9. The method of claim 1 further comprising subjecting the high surface area electrode catalyst to an acid washing process with an inorganic acid to remove a portion of the transition metal from the thermally converted MOF material, wherein the acid washing process improves the electrochemical activity of the high surface area electrode catalyst.

10. The method of claim 9 further comprising a secondary thermal treatment of the electrode catalyst in one of an inert carrier gas and a reductive carrier gas selected from the group consisting of:

NH₃, pyridine, and acetonitrile following the acid washing process.

11. A method of preparing a nitrogen containing electrode catalyst free of precious group metals (PGM), comprising:

synthesizing a metal-organic framework (MOP) electrode catalyst precursor, the MOF electrode catalyst precursor consisting of a plurality of pores, a first non-PGM transition metal chemically bonded with a metal-nitrogen bond to the MOF electrode catalyst precursor, with a multidentate ligand containing nitrogen, and a first organic solvent disposed within the plurality of pores in the MOF electrode catalyst precursor;

wherein the multidentate ligand is selected from the group consisting of imidazolate, pyrazolate, piperazine, tetrazolate, and combinations thereof;

substituting at least a portion of the first organic solvent disposed within the plurality of pores in the MOF electrode catalyst precursor with one of a nitrogen-containing organic solvent and a second non-PGM transition metal; and

thermally activating the MOF electrode catalyst precursor by an elevated temperature treatment to form a plurality of uniformly distributed electrocatalytic active sites.

12. The method of claim 11, wherein the second non-PGM transition metal is different from the first non-PGM transition metal.

13. The method of claim 11, wherein the nitrogen-containing organic solvent is selected from the group consisting of:

dimethylformamide (DMF), diethyformamide (DEF), dimethylacetamide (DMA), cynamide, and pyridine.

14. The method of claim 11 further comprising incorporating the electrode catalyst into a membrane electrode assembly of a proton exchange membrane fuel cell.

15. The method of claim 11 further including a post treatment process comprising:

washing the electrode catalyst in an inorganic acid to remove a portion of the first non-PGM transition metal; and

performing a secondary heat treatment on the electrode catalyst following the acid washing,

wherein the post treatment process enhances the catalytic activity of the electrode catalyst.