Hydrothermal performance of catalyst supports

Patent metadata

Field	Value
Publication number	US-9937490-B2
Application number	US-201414265983-A
Country	US
Kind code	B2
Filing date	Apr 30, 2014
Priority date	Jul 22, 2010
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

A high surface area catalyst with a mesoporous support structure and a thin conformal coating over the surface of the support structure. The high surface area catalyst support is adapted for carrying out a reaction in a reaction environment where the thin conformal coating protects the support structure within the reaction environment. In various embodiments, the support structure is a mesoporous silica catalytic support and the thin conformal coating comprises a layer of metal oxide resistant to the reaction environment which may be a hydrothermal environment.

First claim

What is claimed is:

1. A catalyst system for carrying out a reaction, comprising:
a high surface area mesoporous catalytic support structure characterized by a pre-reaction surface area of between about 100 m 2 /gram and about 1,000 m 2 /gram, the support structure having a plurality of pores, the support structure susceptible to surface area loss within the reaction environment; and
an annealed thin conformal layer comprising at least one metal oxide, metal nitride, or metal sulfide substantially coating the surface of the support structure, the metal oxide, metal nitride, or metal sulfide characterized by a catalytic activity to carry out the reaction and a chemical resistance to the reaction environment greater than the support structure, the thin annealed conformal layer having a threshold thickness wherein structural integrity and catalytic activity of the catalyst system is independent of further increased thickness of the thin annealed conformal layer beyond the threshold thickness,
wherein the thin annealed conformal layer substantially maintains the surface area of the catalyst system within the reaction environment over the duration of the reaction period.

2. The catalyst system of claim 1 , wherein the catalyst system is characterized by a post-reaction surface area loss of less than about 25 percent.

3. The catalyst system of claim 1 , wherein the catalytic support structure comprises a mesoporous silica material.

4. The catalyst system of claim 1 , wherein the metal oxide is selected from the group consisting of: Nb 2 O 5 , TiO 2 and ZrO 2 .

5. The catalyst system of claim 1 , wherein the thin annealed conformal layer is characterized by an average thickness of between about 0.1 nm and about 1.2 nm.

6. The catalyst system of claim 1 , wherein the catalytic support structure comprises a mesoporous silica material, and wherein the thin, annealed conformal layer consists essentially of between about 4 and about 30 monolayers of Nb 2 O 5 .

7. The catalyst system of claim 6 , wherein the reaction environment comprises a hydrothermal environment.

8. A high surface area catalyst support, comprising:
a mesoporous silica support substrate having a plurality of pores and a surface area of between about 100 m 2 /gram and 1,000 m 2 /gram; and
a protective , annealed conformal coating comprising a thickness of between several and about 30 monolayers of at least one metal oxide selected from the group consisting of Nb 2 O 5 , TiO 2 and ZrO 2 , the protective annealed conformal layer substantially coating the surface of the support substrate and configured to substantially prevent structural degradation of the surface area of the support substrate within the hydrothermal reaction environment, the thickness corresponding to a threshold thickness with structural integrity and catalytic performance independent of further increased thickness of the protective annealed conformal layer beyond the threshold thickness.

9. The high surface area catalyst support of claim 8 , wherein the catalyst support is characterized by a catalytic activity, and wherein the catalytic activity is substantially maintained within the hydrothermal reaction environment.

10. The high surface area catalyst support of claim 8 , wherein the support substrate realizes less than about 25 percent surface area loss within the hydrothermal reaction environment.

11. The composition of claim 8 , wherein the protective annealed conformal coating comprises a multiple thin layers of different coating materials of different materials.

12. A composition for catalyzing a reaction comprising:
a high surface area mesoporous catalytic support structure characterized by a pre-reaction surface area of between about 100 m 2 /gram and about 1,000 m 2 /gram, the support structure having a plurality of pores and susceptible to chemical degradation by a reaction environment; and
a thin conformal layer comprising at least one metal oxide, metal nitride, or metal sulfide substantially coating the surface of the support structure, the metal oxide, metal nitride, or metal sulfide, the thin conformal layer being resistant to chemical degradation by the reaction environment, the thin conformal layer having a conformal layer thickness, wherein the conformal layer thicknesses is selected from 0.1 nm to 1.2 nm and corresponds to a threshold thickness with structural integrity and catalytic performance independent of further increased thickness of the thin conformal layer beyond the threshold thickness,
an active catalytic material disposed on the thin conformal layer, the active catalytic material selected from the group consisting of nanoparticles, clusters, or monoatomic species;
wherein the conformal layer stabilizes the mesoporous catalytic support structure to thereby provide hydrothermal stability and maintains the surface area and the porosity of the mesoporous catalytic support structure within the reaction environment for the reaction's duration.

13. The composition for catalyzing a reaction of claim 12 , wherein the composition is characterized by a post-reaction surface area loss of less than about 25 percent.

14. The composition for catalyzing a reaction of claim 12 , wherein the catalytic support structure comprises a mesoporous silica material.

15. The composition for catalyzing a reaction of claim 12 , wherein the metal oxide is selected from the group consisting of: Nb 2 O 5 , TiO 2 and ZrO 2 .

16. The composition for catalyzing a reaction of claim 12 , wherein the catalytic support structure comprises a mesoporous silica material, and wherein the thin conformal layer consists essentially of between about 4 and about 30 monolayers of Nb 2 O 5 .

17. The composition of claim 12 , wherein the thin conformal layer comprises material catalytic to the reaction.

Assignees

• Argonne Nat Laboratory
• Uchicago Argonne Llc

Inventors

• Elam Jeffrey W
• Marshall Christopher L
• Libera Joseph A
• Dumesic James A
• Pagan-Torres Yomaira J

Classifications

• B01J29/78 Primary

  containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium · CPC title

• B01J35/1019

  Operations & Transport · mapped topic

• B01J21/066

  Zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• B01J35/1023

  Operations & Transport · mapped topic

• B01J37/348

  Electrochemical processes, e.g. electrochemical deposition or anodisation · CPC title