Photocatalytic reduction of carbon dioxide to methanol or carbon monoxide using cuprous oxide

• US 10,696,614 B2
• Filed: 12/29/2017
• Issued: 06/30/2020
• Est. Priority Date: 12/29/2017
• Status: Active Grant

• Current Assignee: UChicago Argonne LLC
• Original Assignee: UChicago Argonne LLC
• Inventors: Wu, Yimin, Rajh, Tijana, McNulty, Ian, Liu, Yuzi
• Primary Examiner(s): Smith, Nicholas A
• Assistant Examiner(s): Raphael, Colleen M
• Application Number:
  US15/858,307
• Publication Number:
  US 20190202762A1
• Time in Patent Office: 914 Days
• Field of Search: 2041579, 20415747, 2041575
• CPC Class Codes: B01J 19/123 Ultraviolet light
• CPC Class Codes: B01J 19/127 Sunlight; Visible light
• CPC Class Codes: B01J 2219/0884 Gas-liquid
• CPC Class Codes: B01J 2219/0892 involving catalytically active material
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 27/051 Molybdenum
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/39 Photocatalytic properties
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/088 Decomposition of a metal salt
• CPC Class Codes: B01J 37/10 in the presence of water, e.g. steam
• CPC Class Codes: C01B 32/40 Carbon monoxide
• CPC Class Codes: C01G 3/02 Oxides; Hydroxides
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C07C 29/15 by reduction of oxides of carbon exclusively
• CPC Class Codes: C07C 31/04 Methanol
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

Provided herein are methods of CO₂ reduction to methanol or CO using a Cu₂O catalyst.

Claims

1. A method of converting CO₂ to methanol comprising irradiating CO₂, water, and a catalyst consisting essentially of Cu₂O nanoparticles having a (i i 0) facet to photocatalytically form methanol, wherein i is 1 to 12.

2. The method of claim 1, wherein the irradiating comprises exposure to ultraviolet to visible light.

3. The method of claim 1, wherein the irradiating comprises exposure to light having one or more wavelengths from 200 to 650 nm.

4. The method of claim 1, wherein the water is present as a liquid.

5. The method of claim 1, wherein the water is present as water vapor.

6. The method of claim 1, wherein the (i i 0) facet is a (110) facet.

7. The method of claim 6, wherein the Cu₂O nanoparticles having a (110) facet are octahedral, truncated cubic, or a mixture thereof.

8. The method of claim 7, wherein the irradiating comprises exposure to ultraviolet to visible light.

9. The method of claim 8, wherein the irradiating comprises exposure to light having one or more wavelengths from 200 to 650 nm.

10. The method of claim 1, where the method exhibits a quantum efficiency of at least 50%.

11. The method of claim 10, wherein the quantum efficiency is at least 70%.

12. The method of claim 1, wherein the CO₂ is continuously flowed through a suspension of the Cu₂O nanoparticles in water during the irradiating.

13. The method of claim 1, wherein the Cu₂O nanoparticles having a (i i 0) facet are prepared by a method comprising admixing copper acetate, sodium hydroxide, glucose, and a surfactant and heating the admixture to 60°

C. for 30-90 minutes to form the Cu₂O nanoparticles having a (i i

     0) facet.

14. The method of claim 13, wherein the surfactant comprises sodium dodecyl sulfate.

15. A method of converting CO₂ to CO comprising

irradiating CO₂, water, and a catalyst consisting essentially of MoS₂ adsorbed onto Cu₂O nanoparticles to photocatalytically form CO,

wherein the Cu₂O nanoparticles have a (i i 0) facet, and i is 1 to 12.

16. The method of claim 15, wherein the irradiating comprises exposure to ultravisible to visible light.

17. The method of claim 15, wherein the irradiating comprises exposure to light having one or more wavelengths from 200 to 650 nm.

18. The method of claim 15, wherein the (i i 0) facet is a (110) facet.

19. The method of claim 15, wherein the Cu₂O nanoparticles having a (i i 0) facet are octahedral, truncated cubic, or a mixture thereof.

20. The method of claim 15, wherein the Cu₂O nanoparticles having a (i i 0) facet are prepared by a method comprising admixing copper acetate, sodium hydroxide, glucose, and a surfactant and heating the admixture to 60°

C. for 30-90 minutes to form the Cu₂O nanoparticles having a (i i

     0) facet.