Metal-doped tin oxide for electrocatalysis applications

Patent metadata

Field	Value
Publication number	US-11110433-B2
Application number	US-201716084263-A
Country	US
Kind code	B2
Filing date	Mar 17, 2017
Priority date	Mar 18, 2016
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

The present invention relates to a metal-doped tin oxide which has a BET surface area of at least 30 m 2/g, and comprises at least one metal dopant which is Sb, Nb, Ta, Bi, W, or In, or any mixture thereof, wherein the metal dopant is present in an amount of from 2.5 at % to 25 at %, based on the total amount of tin and metal dopant atoms, and is in a mixed valence state containing atoms of oxidation state OS1 and atoms of oxidation state OS2, wherein the oxidation state OS1 is >0 and the oxidation state OS2 is >OS1 and the atomic ratio of the atoms of OS2 to the atoms of OS1 is from 1.5 to 12.0.

First claim

The invention claimed is:

1. A metal-doped tin oxide which
has a BET surface area of at least 30 m 2 /g, and
comprises a dopant which is Sb,

wherein the metal dopant
is present in an amount of from 2.5 at % to 25 at %, based on the total amount of tin and metal dopant atoms, and
is in a mixed valence state containing Sb 3+ atoms and Sb 5+ atoms, wherein the atomic ratio of Sb 5+ to Sb 3+ , measured by X-ray photoelectron spectroscopy, is from 5.0 to 9.0.

2. The metal-doped tin oxide according to claim 1 , wherein the amount of the metal dopant is from 2.5 at % to 10.0 at %.

3. The metal-doped tin oxide according to claim 1 , wherein the BET surface area of the metal-doped tin oxide is from 30 m 2 /g to 150 m 2 /g and/or the electrical conductivity of the metal doped tin oxide is at least 0.02 S/cm.

4. The metal-doped tin oxide according to claim 1 , wherein the amount of the metal dopant is from 5.0 at % to 7.5 at %.

5. The metal-doped tin oxide according to claim 1 , wherein the BET surface area of the metal-doped tin oxide is from 35 m 2 /g to 110 m 2 /g; and/or the electrical conductivity of the metal doped tin oxide is at least 0.03 S/cm.

6. The metal-doped tin oxide according to claim 1 , wherein the atomic ratio of the Sb 5+ atoms to the Sb 3+ atoms is from 5.0 to 8.0.

7. A process for preparing the metal-doped tin oxide according to claim 1 , comprising
preparing a metal-doped precursor solid by a wet chemical synthesis from a reaction mixture comprising a tin-containing molecular precursor compound and a metal-dopant-containing molecular precursor compound,
subjecting the metal-doped precursor solid to a thermal treatment.

8. The process according to claim 7 , wherein the wet chemical synthesis is a sol-gel process, a chemical precipitation process, a hydrothermal synthesis process, a spray drying process, or any combination thereof.

9. The process according to claim 7 , wherein the tin-containing molecular precursor compound and the metal-dopant-containing molecular precursor compound are mixed at acidic pH, and the pH is subsequently raised by adding a base until the metal-doped precursor solid precipitates; and/or wherein the wet chemical synthesis is carried out in an alcoholic solvent.

10. The process according to claim 7 , wherein the tin-containing molecular precursor compound is a tin salt such as a tin halide or a tin nitrate, or a tin alkoxide, or a mixture thereof; and/or the metal-dopant-containing molecular precursor compound is a metal halide, a metal carboxylate or a metal alkoxide or any mixture thereof.

11. The process according to claim 7 , wherein the wet chemical synthesis is carried out in the presence of a solid additive having a BET surface area of at least 40 m 2 /g.

12. The process according to claim 11 , wherein the solid additive is carbon black or activated carbon, which has a BET surface area of at least 200 m 2 /g.

13. The process according to claim 7 , wherein the thermal treatment includes heating to a temperature of from 400 to 800° C.

14. The process according to claim 11 , wherein the solid additive is carbon black or activated carbon, which has a BET surface area of at least 500 m 2 /g.

15. A composite material, comprising the metal-doped tin oxide according to claim 1 , and an electrocatalyst which is supported on the metal-doped tin oxide.

16. An electrochemical device, comprising the composite material according to claim 15 .

17. The electrochemical device according to claim 16 , wherein the electrochemical device is a polymer electrolyte membrane PEM water electrolyzer or a PEM fuel cell.

18. A catalyst support in an electrochemical device, comprising the metal-doped tin oxide according claim 1 , wherein the electrochemical device is a polymer electrolyte membrane PEM water electrolyzer or a PEM fuel cell.

Assignees

• Basf Se

Inventors

• Peng Xu Yuan
• Ricon-Ovalles Rosalba Adriana
• Venkataraman Shyam Sundar
• Bayer Domnik
• Haas Andreas

Classifications

• Y02E60/36

  Hydrogen production from non-carbon containing sources, e.g. by water electrolysis · CPC title

• H01M4/925

  supported on carriers, e.g. powder carriers · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C25B1/04

  by electrolysis of water · CPC title

• B01J23/14 Primary

  of germanium, tin or lead · CPC title