Hydrothermal performance of catalyst supports
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.
1. A method for preparing using atomic layer deposition (ALD) a catalyst system for carrying out a chemical reaction in a reaction environment detrimental to the structural integrity of a catalytic support structure of the catalyst system, comprising:
providing a catalyst substrate comprising a mesoporous catalytic support structure having a plurality of pores;
providing a first precursor, the first precursor comprising at least one metal;
providing a second precursor, the second precursor comprising an oxygen-containing compound, a nitrogen-containing compound, or a sulfur-containing compound;
depositing on the catalyst substrate a protective conformal layer and having a selected thickness and substantially coating the catalyst substrate wherein the protective conformal layer stabilizes the catalyst substrate to thereby provide hydrothermal stability and maintains the surface area and the porosity of the catalyst substrate within the reaction environment for the reaction and comprising at least one metal oxide, nitride, or sulfide characterized by a chemical resistance to the reaction environment greater than the support structure, the protective conformal layer deposited by performing a plurality of ALD cycles using the ALD reactor, each ALD cycle comprising alternately exposing the catalyst substrate to the first precursor and the second precursor, the method applied to provide the selected thickness being a threshold thickness wherein structural integrity and overall performance of the catalyst system is independent of further increased thickness of the thin conformal layer beyond the threshold thickness; and
depositing at least one additional layer selected from the group of nanoclusters, clusters and a monotonic species having a catalytic activity to carry out the chemical reaction.
2. The method of claim 1 , wherein the protective conformal layer is characterized by a resistance that maintains the surface area of the catalyst system within the reaction environment to within at least about 75 percent of the pre-reaction surface area.
3. The method of claim 1 , further comprising reducing the diameter of the plurality of pores by selecting the number of ALD cycles to obtain a reduced pore diameter configured to selectively exclude from the plurality of pores at least one reactant in the reaction environment, and wherein the catalyst system is provided with a molecular sieve characterized by the reduced pore diameter.
4. The method of claim 1 , wherein the at least one metal of the first precursor is selected from the group consisting of: Nb, Ti and Zr.
5. The method of claim 4 , wherein the oxygen-containing compound is selected from the group consisting of: water vapor, H 2 O 2 , ozone, nitrous oxide, and oxygen;
wherein the nitrogen-containing compound is selected from the group consisting of: ammonia, hydrazine, and substituted hydrazines; and
wherein the sulfur containing compound is H 2 S.
6. The method of claim 1 , wherein the protective conformal layer is characterized by an average thickness of between about 0.1 nm and about 1.2 nm.
7. The method of claim 1 , wherein the catalyst system comprises a mesoporous silica support structure and a Nb 2 O 5 protective conformal layer deposited by performing between about 1 and about 30 ALD cycles.
8. The method of claim 7 , wherein the reaction environment comprises a hydrothermal environment.
9. The method of claim 1 , further comprising depositing an additional metal oxide, metal nitride, or metal sulfide on the catalyst substrate by performing at least one ALD cycle alternately exposing the catalyst substrate to a third precursor and a fourth precursor, wherein the additional metal oxide alters at least one of the catalytic activity and the resistance to the reaction environment of the catalytic system.