IP Library Granted Patent US 11,033,888
Granted Patent B2
US 11,033,888 · App. 16/116,662 · Granted Jun 15, 2021

Nanofiber electrocatalyst

Inventors: Di-Jia Liu (Elmhurst, IL); Lina Chong (Naperville, IL)
Assignee: UChicago Argonne, LLC
B01J31/1691B01J21/185B01J23/10B01J23/20B01J23/28B01J23/34B01J23/745B01J23/75B01J23/83B01J23/8871B01J27/24B01J35/002B01J35/0033B01J35/06B01J35/1014B01J35/1019B01J35/1023B01J35/1057B01J35/1061B01J37/04B01J37/084B01J37/348C08L23/0853C08L33/12C08L33/20C08L39/06C08L75/04C08L77/00B01J31/181B01J2531/11B01J2531/36B01J2531/37B01J2531/38B01J2531/48B01J2531/57B01J2531/58B01J2531/64B01J2531/66B01J2531/72B01J2531/842B01J2531/845B01J2531/847B82Y30/00B82Y40/00C08L77/06
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Quick Facts
Patent No.
US 11,033,888
App. No.
16/116,662
Granted
Jun 15, 2021
Kind
B2
Abstract

A nanofibrous catalyst for in the electrolyzer and methods of making the catalyst. The catalysts are composed of highly porous transition metal carbonitrides, metal oxides or perovskites derived from the metal-organic frameworks and integrated into a 3D porous nano-network electrode architecture. The catalysts are low-cost, highly active toward OER, with excellent conductivity yet resistant to the oxidation under high potential operable under both acidic and alkaline environments.

Claims (30)

1. A method comprising:

preparing a metal organic framework material comprising MOF crystals forming a mixture of MOF crystals suspended in a polymer solution, the MOF crystals being bimetallic or trimetallic;

electrospinning the MOF crystals and polymer mixture, forming porous and interconnected nanofibers having MOF crystals uniformly dispersed; and

subjecting the metal organic framework containing porous nanofiber to sequential thermolysis, forming catalytic nanofibers with uniformly distributed catalytic sites;

wherein the catalytic nanofibers are catalytic for the oxygen evolution reaction for water splitting in either alkaline or acidic aqueous media.

2. The method of claim 1 , wherein the polymer solution comprises a polymer selected from the group consisting of polyacrylonitrile (PAN), poly(methylmethacrylate) (PMMA), polyvinylpyrrolidone (PVP), nylon6,6 (PA-6,6), polyurethanes (PU), polybenzimidazole (PBI), polycarbonate (PC), polyethylene-co-vinyl acetate (PEVA), collagen (PEO), polyacrylic acid-polypyrene methanol (PAA-PM), and polymethacrylate (PMA).

3. The method of claim 2 , wherein concentration of the MOF crystals suspended in the polymer solution is from 0.1 mg/ml to 0.6 mg/ml.

4. The method of claim 3 , wherein concentration of the MOF crystals suspended in the polymer solution is from 0.4 mg/ml to 0.6 mg/ml.

5. The method of claim 3 , wherein concentration of the MOF crystals suspended in the polymer solution is from 0.1 mg/ml to 0.3 mg/ml.

6. The method of claim 1 , wherein the metal organic framework comprises a transition metal selected from the group consisting of Co, Fe, Mn, Mo, Li, Nb, Ta, Zr, and Y.

7. The method of claim 6 , wherein forming catalytic nanofibers comprises forming the uniformly distributed catalytic sites to include the transitional transition metal.

8. The method of claim 1 , wherein forming the catalytic nanofibers comprises forming transition metal interconnected structures extending between the uniformly distributed catalytic sites.

9. The method of claim 1 , wherein the thermolysis comprises a first thermal conversion under inert environment at a first temperature between 750° C. to 1100° C. for a first period of time between one to four hours, then a second thermal conversion under oxidizing environment at a second temperature between 200° C. to 500° C. for a period of 30 minutes to 2 hours, then a third thermal conversion under a reducing environment at a third temperature between 200° C. and 500° C. for a third period of 30 minutes to 2 hours, wherein the catalytic nanofibers are catalytic for oxygen evolution reaction in alkaline media.

10. The method of claim 1 , wherein the thermolysis comprises a first thermal conversion at a temperature between 250° C. and 500° C. under an oxidizing environment for a first period of time of 30 minutes to 10 hours, wherein the catalytic nanofibers are catalytic for oxygen evolution reaction in acidic media.

11. A method comprising:

preparing a metal organic framework material comprising MOF crystals forming a mixture of MOF crystals suspended in a polymer solution;

electrospinning the MOF crystals and polymer mixture, forming porous and interconnected nanofibers having MOF crystals uniformly dispersed; and

subjecting the metal organic framework containing porous nanofiber to sequential thermolysis, forming catalytic nanofibers with uniformly distributed catalytic sites;

wherein the thermolysis comprises:

a first thermal conversion under inert environment at a first temperature between 750° C. to 1100° C. for a first period of time between one to four hours,

then a second thermal conversion under oxidizing environment at a second temperature between 200° C. to 500° C. for a period of 30 minutes to 2 hours, and

then a third thermal conversion under a reducing environment at a third temperature between 200° C. and 500° C. for a third period of 30 minutes to 2 hours,

wherein the catalytic nanofibers are catalytic for oxygen evolution reaction in alkaline media, and

wherein the catalytic nanofibers are catalytic for the oxygen evolution reaction for water splitting in either alkaline or acidic aqueous media.

12. A method comprising:

preparing a metal organic framework material comprising MOF crystals forming a mixture of MOF crystals suspended in a polymer solution;

electrospinning the MOF crystals and polymer mixture, forming porous and interconnected nanofibers having MOF crystals uniformly dispersed; and

subjecting the metal organic framework containing porous nanofiber to sequential thermolysis, forming catalytic nanofibers with uniformly distributed catalytic sites;

wherein the thermolysis comprises a first thermal conversion at a temperature between 250° C. and 500° C. under an oxidizing environment for a first period of time of 30 minutes to 10 hours, wherein the catalytic nanofibers are catalytic for oxygen evolution reaction in acidic media, and

wherein the catalytic nanofibers are catalytic for the oxygen evolution reaction for water splitting in either alkaline or acidic aqueous media.

Assignments (2)
CONFIRMATORY LICENSE Recorded Jun 7, 2021
From: UCHICAGO ARGONNE, LLC
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 056454/0515 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 23, 2019
From: CHONG, LINA; LIU, DI-JIA
To: UCHICAGO ARGONNE, LLC
Reel/Frame 049841/0287 →
Continuity (2)
Provisional Application 62552340 · Aug 30, 2017
Related Publication 20190060888A1 · Feb 28, 2019
Cited By (2)
US 12,269,020 US 12,435,429