The invention relates generally to the field of nanoreactors formed of ceramic compositions. More specifically, the invention relates to ceramic nanoreactors with architecturally engineered parameters and methods for making the same.
Membranes having pores that possess a tightly controlled size distribution that is in the nanoscale length range are known to be useful as filters for separations, catalytic hosts, and sensor components. Such membranes may be produced using surfactant-templated approaches. A tightly controlled size distribution is desirable in that it provides a diffusion profile having reduced dispersion relative to a broader size distribution. Such membranes are useful in reactive separations, water purification, or removal of heavy metals and/or biological contaminants. Moreover, a tightly controlled size distribution is useful for size-based exclusion. Such membranes are useful in a variety of applications, such as, for example, in filters for separations.
In the design of chemical reactors, control over material flow through the reactor is important for assuring a desired degree of selectivity and/or conversion. For example, uncontrolled fluid bypass decreases, and stagnant regions increase, the time a molecule remains in the reactive region. In multi-step reactions, it is often advantageous to guide the material progressively through reactive regions that each promote a step in the overall reaction. This can be accomplished by engineering the fluid transport through the structure of the reactor.
It is known to architecturally engineer parameters of ceramic structures. See, for example, U.S. patent application Ser. No. 10/983,277, filed Nov. 8, 2004 with a priority date of May 28, 2004, and entitled “Ceramic Structures and Methods of Making Them,” commonly owned by assignee of the present patent application.
It is desirable to utilize architecturally engineered ceramic structures to form nanoreactor assemblies capable of performing chemical reactions in the nanoscale.
Embodiments of the invention provide a nanoreactor assembly that includes a ceramic structure comprising at least one opening therethrough and a porous filler material that has a plurality of regions and is disposed within the at least one opening. Each region is architecturally engineered to include at least one specific pore architecture, and the specific pore architectures are chosen to enable a chemical process to be performed within the ceramic structure.
One aspect of the invention provides a nanoreactor assembly that includes a scaffold with openings, and a porous filler material. The porous filler material includes a plurality of regions, is disposed within the openings, and includes at least one doped or undoped composition from the group consisting of an oxide, a borate, an aluminate, a silicate, a phosphate, and any combination thereof. Each of the regions is architecturally engineered to include at least one specific pore architecture. The specific pore architectures are chosen to enable a chemical process to be performed within the membrane.
Embodiments of the invention provide a method for performing a chemical process within a nanoreactor assembly. The method includes providing a ceramic structure that includes at least one opening therethrough, introducing a porous filler material into the at least one opening, and introducing at least one chemical to the nanoreactor assembly. The porous filler material includes a plurality of regions and each of the regions includes at least one specific pore architecture chosen to enable a chemical process to be performed within the ceramic structure.
These and other advantages and features will be more readily understood from the following detailed description of preferred embodiments of the invention that is provided in connection with the accompanying drawings.
a is a cross-sectional view taken along line IVa-IVa of
b is a plan view showing porous filler material in the structure of
a-5b are close-up plan views showing multiple regions of different pore connectivity in accordance with an embodiment of the invention.
a-6b are cross-sectional views showing multiple regions of different pore connectivity in accordance with an embodiment of the invention.
a-7f illustrate various components for a nanoreactor having a cubic architecture in accordance with an embodiment of the invention.
a illustrates a hybrid component for a nanoreactor having both cubic and hexagonal architectures in accordance with an embodiment of the invention.
b illustrates an array of the hybrid components of
a illustrates a nanoreactor assembly constructed in accordance with an embodiment of the invention.
b illustrates a nanoreactor assembly constructed in accordance with an embodiment of the invention.
a schematically illustrates a multi-region nanoreactor assembly constructed in accordance with an embodiment of the invention.
b schematically illustrates a multi-region nanoreactor assembly constructed in accordance with an embodiment of the invention.
The scaffold 22 provides mechanical stability. An example of a suitable scaffold 22 includes an anodic aluminum oxide (AAO) membrane with openings 24. The scaffold 22 may be formed of various materials such as glass, silica microfiber filter, quartz, and compacted ceramic powders. The scaffold 22 may be of any shape and size, such as depth, width, length, or other dimension.
The number of openings 24 in a scaffold 22 may vary. Each opening 24 may be independent of another opening 22. For example, each opening 24 may independently be filled with a porous filler material 26 independent of the porous filler material 26 that may fill another opening 24. Furthermore, the portion of an opening 24 filled with a porous filler material 26 may be independent of the portion of another opening 24 filled with a porous filler material 26.
The porous filler material 26 has a plurality of pores. The pores have an average size in a range from about 2 nm to about 100 nm. The pore size can be inferred from nitrogen adsorption measurements using a model for the adsorption process, such as for example, the Barrett-Joyner-Halenda (BJH) analysis. The term “nanoporous” as used herein means pores having a size in a range from about 1 nm to about 100 nm. Specifically, according to IUPAC, the pores are referred to as micropores when the pores are less than 2 nm. The pores are referred to as mesopores or mesoporous when the pores are in a size range from 2 nm to 50 nm. The pores are referred to as macropores or macroporous when the pores are in a size range greater than 50 nm.
The porous filler material 26 may be architecturally engineered so as to form more than one pore architecture. A pore architecture means a plurality of pores having a size distribution (also referred as size range) and an organization. For each pore architecture, the average pore size distribution does not vary by more than about 100% when the average pore size is in a range from about 2 nm to about 50 nm (i.e. mesoporous). The average pore size distribution does not vary by more than about 50% when the average pore size is greater than about 50 nm (i.e. macroporous). The pores comprise at least two pore architectures when the porous filler material 26 is a single silica composition (i.e. only silica composition). Pore organization refers to the type of pore phase in the porous filler material 26, and can assume periodic and non-periodic arrangements, as determined by diffraction (X-ray, neutron, synchrotron), microscopy (transmission electron, scanning electron), and spectroscopic (electron energy loss) techniques. Examples of pore organization include, but are not limited to, hexagonal organization, cubic organization, lamellar organization, bicontinuous organization, worm-like organization, ribbon organization, mesh organization, and gyroid organization.
The porous filler material 26 comprises at least one wall composition. In one embodiment, the composition of the porous filler material 26 may either comprise an oxide, a borate, an aluminate, a silicate, and a phosphate, individually or in any combination thereof. In one embodiment, the porous filler material 26 comprises an oxide. Examples of oxides include, but are not limited to, SiO2, TiO2, Al2O3, ZrO2, Nb2O3, Ta2O5WO3, SnO2, HfO2, SrAlO3, SiTiO4, ZrTiO4, Al2TiO5, ZrW2O8, CeO2, yttria stabilized zirconia, Y2O3, in their stoichiometric or non-stoichiometric forms, either individually or in any combination thereof. In one embodiment, the porous filler material 26 includes a plurality of compositions. The plurality of compositions may comprise any combination of the materials listed above. Furthermore, the composition may be doped with a lanthanide, a transition metal, or any combination thereof. Dopings may induce optical emission within the wall of the filler material by impurity-activated luminescence. Impurity-activated luminescence occurs when a non-luminescent host material has been modified by inclusion of an activator species (i.e., a dopant) which is typically present in the host material in a relatively low concentration, such as, for example, from about 200 parts per million to 1 part per thousand. However, some materials require several mole or atomic percentage of dopant ions for optimized optical properties. With an impurity-activated luminescent material, the activator ions may either absorb the incident photons directly, or the lattice may absorb the incident photons and transfer the absorbed photon energy to the dopant ions. Examples of such dopants include, but are not limited to, Ce, Pr, Nd, Eu, Th and Cr. Furthermore, the porous filler material may include a portion or the total number of pores being functionalized with compositions necessary to promote/enhance chemical processes. Examples of pore functionalizing materials include, but are not limited to, palladium, platinum, gold, iridium, rhodium, ruthenium, and rhenium. In one embodiment, the porous filler material 26 fills at least 50% of each opening 24. In another embodiment, a portion of an opening 24 is unfilled by the porous filler material 26.
a is an expanded cross-sectional view of the ceramic structure 20 of
Next will be described, with specific reference to
Nanoreactors enable control to be exerted over conversion and selectivity. For example, the conversion of a heterogeneous (catalyzed) reaction is a function of the residence time of the chemical mixture. Longer residence times allow a reaction to approach equilibrium conversion. In nanoreactors, it is possible to obtain greater than equilibrium conversion by removing one of the products as the reaction is occurring.
Another advantage of nanoreactors is control over selectivity. In some cases, several possible products may be possible from a given set of reagents for a known catalyst. The selectivity can be tuned by the relative concentrations of the reagents, or through the residence time in the catalytic region. In nanoporous materials, it is possible to shrink the residence time to access new regimes. Specifically, for nanoporous regions of size 100 nm, it is possible to get residence times less than microseconds. It should be appreciated that along with the ability for chemical processing within the membrane 22 is the ability for energy transfer. For example, during a chemical reaction, often there is a change in energy state, either an exothermic change or an endothermic change. Depending upon the circumstances of the desired chemical processing, the nanoreactor assembly can be configured to take into account the energy transfer component. For example, relative sizes of regions may be tuned to produce and consume heat in order to drive an effectively isothermal process. Additionally, the inclusion of an external stimulus, for example, an externally driven electric field, can drive an electrolyte solution through the nanoreactor assembly.
A nanoreactor assembly 65 is schematically illustrated in
For purposes of illustrative description only, next will be described specific examples of chemical processing that may be performed within a nanoreactor assembly, such as those described herein. A chemical mixture of two chemicals, A and B, is added to a nanoreactor assembly. The molecules of chemical A are smaller than those of chemical B, but more reactive. Thus, the concentration of chemical A must be kept low to inhibit side reactions. The chemical mixture of A+B is added to the architecture 26b, which contains a catalyst for the equation A+B→C. As the chemical mixture of A+B transports through the architectures, the mixture becomes depleted in the chemicals A and B, but enriched in the chemical C. Chemical A is more dilute than chemical B because chemical A is highly reactive, so keeping it in low concentrations prevents side reactions. Since chemical A is more dilute than chemical B, it will become depleted sooner than chemical B. However, if architecture 26a contains pores small enough to exclude chemicals B and C, but large enough to allow transport of chemical A, a greater amount of chemical A can be delivered to the chemical mixture, therefore allowing a greater conversion rate. While the key benefit of pore size in this example is conversion rate, such tuning also improves selectivity.
Specific examples of chemicals A, B and C may include:
A=H2;
B═CxH2x; and
C═CxH2x+2.
The above example of chemicals would allow a hydrogenation reaction to occur within the nanoreactor assembly. Alternatively, if a feed chemical C═CxH2x+2 is added to the nanoreactor assembly, a dehydrogenation reaction (C→A+B) can occur within the nanoreactor assembly, where A=H2 and B═CxH2x. The chemical C may be selectively removed by transport through architecture 26b.
Next, with reference to
It should also be appreciated that the pore architectures of embodiments of the nanoreactor assembly may be tuned to enable the chemical process to be performed within the ceramic structure 22. The tuning may include adjusting one or more of the following: (a) pore size within the porous filler material, (b) the type of pore architecture, (c) the size of the regions, (d) the number of regions, (e) the number and type of pore architectures per each region, (f) the composition of the walls of the at least one opening, (g) the presence of a functionalizing treatment on the walls of the at least one opening or in pores of the porous filler material, and (h) the connectivity between the regions.
Next, with specific reference to
Referring specifically to
While the invention has been described in detail in connection with only a limited number of embodiments, it should be readily understood that the invention is not limited to such disclosed embodiments. Rather, the invention can be modified to incorporate any number of variations, alterations, substitutions or equivalent arrangements not heretofore described, but which are commensurate with the spirit and scope of the invention. For example, while embodiments of the invention have been described as including a ceramic structure, it should be appreciated that structures formed of other materials may be suitable, such as, hybrid materials, polymers, and metals. Additionally, while various embodiments of the invention have been described, it is to be understood that aspects of the invention may include only some of the described embodiments. Accordingly, the invention is not to be seen as limited by the foregoing description, but is only limited by the scope of the appended claims.