Electrochemical cells for direct oxide reduction, and related methods
US-2023282378-A1 · Sep 7, 2023 · US
US12359333B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-12359333-B2 |
| Application number | US-202318459966-A |
| Country | US |
| Kind code | B2 |
| Filing date | Sep 1, 2023 |
| Priority date | Sep 2, 2022 |
| Publication date | Jul 15, 2025 |
| Grant date | Jul 15, 2025 |
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A metal-coated article that comprises a substrate, a transition metal region adjacent to the substrate, and a platinum-group metal region adjacent to the transition metal region. The transition metal region comprises a transition metal carbide layer adjacent to the substrate. The platinum-group metal region comprises a transition metal/platinum-group metal layer that is adjacent to the transition metal region and a platinum-group metal layer adjacent to the transition metal/platinum-group metal layer. Related methods are also disclosed.
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What is claimed is: 1. A method of forming a metal-coated article, comprising: electrodepositing a transition metal layer onto a substrate; and converting at least a portion of the transition metal layer to a transition metal carbide layer to form a transition metal region; and electrodepositing a platinum-group metal layer on the transition metal region; and converting at least a portion of the platinum-group metal layer to a transition metal/platinum-group metal layer on the platinum-group metal layer to form a platinum-group metal region. 2. The method of claim 1 , wherein electrodepositing a transition metal layer onto a substrate comprises electrodepositing the transition metal layer at a temperature in a range of from about 350° C. to about 500° C. 3. The method of claim 2 , wherein electrodepositing a transition metal layer onto a substrate comprises electrodepositing the transition metal layer from an electrolyte comprising LiBr, KBr, and CsBr. 4. The method of claim 1 , wherein electrodepositing a platinum-group metal layer onto the transition metal region comprises electrodepositing the platinum-group metal layer from an alkali halide salt electrolyte at a temperature in a range of from about 350° C. to about 500° C. 5. The method of claim 4 , wherein electrodepositing the platinum-group metal layer from an alkali halide salt electrolyte comprises electrodepositing the platinum-group metal layer from an electrolyte comprising LiBr, KBr, and CsBr. 6. The method of claim 1 , wherein converting at least a portion of the transition metal layer to a transition metal carbide layer comprises annealing the substrate and the transition metal layer at a temperature from about 500° C. to about 600° C. 7. The method of claim 1 , wherein converting at least a portion of the platinum-group metal layer to a transition metal/platinum-group metal layer comprises annealing the transition metal region and the platinum-group metal layer at a temperature from about 500° C. to about 600° C. 8. A method of forming a metal-coated article, comprising: forming an as deposited transition metal layer on a substrate; annealing the as deposited transition metal layer to convert at least a portion of the as deposited transition metal layer to a transition metal carbide layer; forming an as deposited platinum-group metal layer on the transition metal carbide layer; and annealing the as deposited platinum-group metal layer to convert at least a portion of the as deposited platinum-group metal layer to a transition metal/platinum-group metal layer. 9. The method of claim 8 , wherein annealing the as deposited transition metal layer to convert at least a portion of the as deposited transition metal layer comprises converting substantially all of the as deposited transition metal layer to the transition metal carbide layer. 10. The method of claim 8 , wherein annealing the as deposited platinum-group metal layer to convert at least a portion of the as deposited platinum-group metal layer to a transition metal/platinum-group metal layer comprises forming the platinum-group metal layer and a platinum-group metal layer. 11. A method of forming a metal-coated article, comprising: electrodepositing one or more transition metal layers onto a substrate layer from an electrolyte comprising an alkali metal halide; and converting at least a portion of the one or more transition metal layers to a transition metal carbide layer to form a transition metal region; and electrodepositing one or more platinum-group metal layers on the transition metal region; and converting at least a portion of the one or more platinum-group metal layers to a transition metal/platinum-group metal layer on the platinum-group metal layer to form a platinum-group metal region. 12. The method of claim 11 , wherein converting at least a portion of the one or more transition metal layers to a transition metal carbide layer to form a transition metal region comprises converting at least a portion of the one or more transition metal layers to a transition metal carbide layer exhibiting a substantially homogenous chemical composition. 13. The method of claim 11 , wherein converting at least a portion of the one or more transition metal layers to a transition metal carbide layer to form a transition metal region comprises converting at least a portion of the one or more transition metal layers to a transition metal carbide layer exhibiting a gradient of carbon in the transition metal carbide layer. 14. The method of claim 11 , wherein converting at least a portion of the one or more transition metal layers to a transition metal carbide layer to form a transition metal region comprises converting at least a portion of the one or more transition metal layers to a transition metal carbide layer to form a transition metal region comprising a transition metal layer and a transition metal carbide layer, wherein a relative thickness of the transition metal carbide layer is greater than a relative thickness of the transition metal layer. 15. The method of claim 11 , wherein converting at least a portion of the one or more transition metal layers to a transition metal carbide layer to form a transition metal region comprises converting at least a portion of the one or more transition metal layers to a transition metal carbide layer to form a transition metal region comprising a transition metal layer and a transition metal carbide layer, wherein a ratio of a thickness of the transition metal carbide layer to a thickness of the transition metal layer is about 3:1. 16. The method of claim 11 , wherein electrodepositing one or more platinum-group metal layers on the transition metal region comprises electrodepositing one or more of platinum, palladium, rhodium, iridium, ruthenium, and osmium. 17. The method of claim 11 , wherein electrodepositing one or more platinum-group metal layers on the transition metal region comprises electrodepositing one or more of ruthenium and osmium. 18. The method of claim 11 , wherein converting at least a portion of the one or more platinum-group metal layers to a transition metal/platinum-group metal layer on the platinum-group metal layer to form a platinum-group metal region comprises converting at least a portion of the one or more platinum-group metal layers to a transition metal/platinum-group metal layer exhibiting a homogeneous chemical composition of the transition metal and the platinum-group metal. 19. The method of claim 11 , wherein converting at least a portion of the one or more platinum-group metal layers to a transition metal/platinum-group metal layer on the platinum-group metal layer to form a platinum-group metal region comprises converting at least a portion of the one or more platinum-group metal layers to a transition metal/platinum-group metal layer exhibiting a heterogeneous chemical composition of the transition metal and the platinum-group metal. 20. The method of claim 11 , wherein converting at least a portion of the one or more platinum-group metal layers to a transition metal/platinum-group metal layer on the platinum-group metal layer to form a platinum-group metal region comprises converting at least a portion of the one or more platinum-group metal layers to a transition metal/platinum-group metal layer that exhibits a chemical composition that transitions between a chemical composition of the transition metal region and a chemical composition of the platinum-group metal region.
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