Nanomaterial-based adsorption processing and catalysis

Abstract

A method comprising contacting an initial sample having an initial concentration of urea in solution with a composition comprising metal oxide nanofilaments under conditions such that at least a portion of the urea is adsorbed onto the metal oxide nanofilaments resulting in a final concentration of urea in the solution, the metal oxide nanofilaments optionally comprising titanium. An apparatus for removing urea from an initial aqueous solution of urea, the apparatus comprising a replaceable cartridge of a metal oxide nanofilament composition through which the initial aqueous solution of urea is directed to pass, the cartridge being adapted for contacting the metal oxide nanofilaments with the initial sample comprising metal ions and / or metals under conditions such that at least a portion of the metal ions and / or metals become associated with the metal oxide nanofilaments.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to and the benefit of U.S. Patent Application No. 63 / 309,391, entitled "Nanomaterial-Based Adsorption Processing and Catalysis," filed February 11, 2022. All of the foregoing applications are incorporated by reference herein in their entireties for all purposes.

[0002] The present disclosure relates to the field of two-dimensional materials. [Background technology]

[0003] The removal of certain undesirable chemical species (e.g., urea) from samples is an important process with applications in industry, medicine, and the environment. However, such adsorption can be difficult to achieve in a consistent and effective manner. Thus, there is a need for materials capable of adsorbing undesirable species from samples, solutions, and suspensions, and methods for effectively accomplishing such adsorption. Summary of the Invention

[0004] To meet the stated needs, the present disclosure provides a method comprising contacting an initial sample having an initial concentration of urea in solution with a composition comprising metal oxide nanofilaments under conditions such that at least a portion of the urea is adsorbed onto the metal oxide nanofilaments, resulting in a final concentration of urea in the solution, the metal oxide nanofilaments optionally comprising titanium, the metal oxide nanofilaments optionally comprising carbon, the metal oxide nanofilaments having an anatase or lepidocrocite structure, and further optionally irradiating the composition and the urea with light. The oxide nanofilaments can be metal oxide nanofilaments having a one-dimensional lepidocrocite (1DL) structure. Such a method can be used, for example, in dialysis applications for patients suffering from kidney disease.

[0005] Also provided is an apparatus for removing urea from an initial aqueous solution of urea, the apparatus comprising a replaceable cartridge of a metal oxide nanofilament composition through which the initial aqueous solution of urea is guided, the cartridge being adapted to contact the metal oxide nanofilaments contained therein, the metal oxide nanofilaments optionally comprising titanium, the metal oxide nanofilaments optionally comprising carbon, and the oxide nanofilaments optionally having an anatase structure. Such an apparatus can be used, for example, in dialysis applications.

[0006] Also provided is a method comprising contacting a composition comprising metal oxide nanofilaments with an initial sample comprising metal ions and / or a metal under conditions such that at least a portion of the metal ions and / or metal become associated with the metal oxide nanofilaments, the metal oxide nanofilaments optionally comprising titanium, the metal oxide nanofilaments optionally having an anatase structure or a lepidocrocite structure, and optionally irradiating the composition and the metal oxide nanofilaments and / or metal.

[0007] Additionally, a composition is provided that includes metal oxide nanofilaments having at least two salts.

[0008] Further provided is a method of contacting (i) a composition comprising metal oxide nanofilaments with at least one metal of a metal salt associated therewith and (ii) a solution, said metal oxide nanofilaments optionally comprising titanium, said metal oxide nanofilaments optionally having an anatase structure or a lepidocrocite structure, wherein the metal of the metal salt can be different from the metal of the metal oxide nanofilaments. [Brief description of the drawings]

[0009] In the drawings, which are not necessarily drawn to scale, like numbers may represent like components in different views. Like numbers with different letter suffixes may represent different instances of the like components. The drawings illustrate generally, by way of example, but not by way of limitation, various aspects discussed in the present specification.

[0010] [Figure 1] Figure 1 shows the oxygen evolution reaction polarization curves in 0.1 M KOH for TCO (gray), TCO+Ni (green), TCO+Ni / Fe (red), and a commercial IrO2 catalyst (black). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present disclosure may be understood more readily by reference to the following detailed description of the preferred embodiments and the examples included therein.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In case of conflict, the present specification, including definitions, shall prevail. Preferred methods and materials are described below, but methods and materials similar or equivalent to those described herein may be used in the practice or testing. All publications, patent applications, patents and other documents described herein are incorporated by reference in their entirety. The materials, methods and examples disclosed herein are illustrative only and are not intended to be limiting.

[0013] The singular forms "a," "an," and "the" include plural referents unless the context clearly indicates otherwise.

[0014] As used herein and in the claims, the term "comprising" may include the embodiments "consisting of" and "consisting essentially of." As used herein, the terms "comprise(s), "include(s), "having(s), "has(s), "can(s), "contain(s)," and variations thereof, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named components / steps and allow for the presence of other components / steps. However, such descriptions should also be construed as describing compositions or steps as "consisting of" and "consisting essentially of" the listed components / steps, which allows for only the named components / steps to be present along with impurities that may result therefrom, and excludes other components / steps.

[0015] As used herein, the terms "about" and "at or about" mean that the quantity or value in question may be approximately or approximately the same as the other value specified. As used herein, it is generally understood to be a variation of ±10% of the nominal value unless otherwise indicated or inferred. The term is intended to convey that similar values ​​promote the same results or effects as described in the claims. That is, it is understood that the amounts, sizes, formulations, parameters, and other quantities and characteristics are not and do not have to be precise, but can be approximated and / or larger or smaller as desired, reflecting tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art. In general, the amounts, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate", whether or not they are expressly stated as such. When "about" is used before a quantitative value, it is understood that the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0016] Unless otherwise indicated to the contrary, numerical values ​​should be understood to include numerical values ​​that are the same when reduced to the same significant figures, and numerical values ​​that differ from the stated value by less than experimental error using conventional measuring techniques of the type described herein to determine the numerical value.

[0017] All ranges disclosed herein are inclusive of the recited endpoints and are independent of the endpoints (e.g., "between 2 grams and 10 grams, and all intermediate values, including 2 grams, 10 grams, and all intermediate values"). The endpoints of the ranges and any values ​​disclosed herein are not limited to the exact ranges or values, but are sufficiently imprecise to include values ​​that are close to these ranges and / or values. All ranges are combinable.

[0018] As used herein, approximation may be applied to modify any quantitative expression that may vary without resulting in a change in the basic function to which it is related. Thus, a value modified by terms such as "about" or "substantially" may in some cases not be limited to the exact value specified. At least in some cases, an approximation may correspond to the precision of an instrument for measuring the value. The modifier "about" should also be considered to disclose a range defined by the absolute values ​​of the two endpoints. For example, the phrase "from about 2 to about 4" also discloses the range "from 2 to 4". The term "about" may refer to plus or minus 10% of the indicated numerical value. For example, "about 10%" may indicate a range of 9% to 11%, and "about 1" may mean 0.9 to 1.1. Other meanings of "about" may be apparent from the context, such as rounding, so for example, "about 1" may mean 0.5 to 1.4. Additionally, the term "comprising" should be understood to have the open-ended meaning of the term "including," but also includes the closed meaning of the term "consisting." For example, a composition consisting of components A and B may be a composition containing A, B, and other components, but may also be a composition consisting only of A and B. All documents cited herein are incorporated by reference in their entirety for all purposes. EXAMPLES

[0019] Working Example The following examples are illustrative, and do not limit the scope of the disclosure or the appended claims.

[0020] Provided herein is one example of a methodology for enhancing the catalytic capabilities of TCO materials by incorporating various metal species through an exchange process.

[0021] Without being bound to a particular theory, the exchange process can involve convective mixing of the colloidal TCO material in an aqueous solution containing one or more inorganic / organic salts of the transition metal species. Convective agitation without the application of external driving forces such as temperature, potential, reactants, or reducing agents results in a self-limiting incorporation of the transition metal into the TCO material. This occurs with or without the exchange of Ti atoms in the matrix. Analysis of the composition of the material shows that the new transition metal is not simply intercalated as an ion between the layers. Electrochemical redox behavior indicates that the new transition metal is a reduced species. This exchange process does not occur in other oxide materials, indicating that there are aspects of the TCO that favor this exchange and incorporation of the reduced metal species into the material. This process is suitable for a variety of metals, including transition metals with equilibrium potentials higher than titanium. The process has been demonstrated to be self-limiting, as the amount of metal exchange and the overall performance of the material do not change with increasing time of the exchange process.

[0022] After TCO synthesis, Ni and Ni / Fe are incorporated into the TCO material. Figure 1 shows the effect of Ni and Ni / Fe additives on the TCO by measuring the activity of the material towards the oxygen evolution reaction (OER). After the addition of Ni, the activity of the TCO increased significantly over the plain TCO, as measured by the increase in current at potentials above 1.23 V vs. the reversible hydrogen electrode (RHE). Incorporation of both Ni and Fe into the TCO using the described exchange process further improves the OER performance. For comparison, IrO2, a currently industrially used OER catalyst, is plotted. The Ni / Fe incorporated TCO showed OER performance comparable to the current industrial state of the art. This result demonstrates the utility of the described approach in tailoring the catalytic performance of TCO materials.

[0023] Aspects The following aspects are illustrative and not limiting of the scope of the disclosure or the appended claims. Any part or portion of any one or more aspects can be combined with any part or portion of any one or more other aspects.

[0024] Aspect 1. A method comprising contacting an initial sample having an initial concentration of urea in solution with a composition comprising metal oxide nanofilaments under conditions such that at least a portion of said urea is adsorbed onto said metal oxide nanofilaments resulting in a final concentration of urea in said solution, said metal oxide nanofilaments optionally comprising titanium, said metal oxide nanofilaments optionally comprising carbon, said metal oxide nanofilaments having an anatase structure or a lepidocrocite structure, and further optionally irradiating said composition and said urea with light.

[0025] Titanium oxide nanofilaments are believed to be particularly suitable. Examples of one-dimensional nanofilaments are described in Badr et al., "Bottom-Up, Scalable Synthesis Of Anatase Nanofilament-Based Two-Dimensional Titanium Carbo-Oxide Flakes," Materials Today 2021 (https: / / doi.org / 10.1016 / j.mattod.2021.10.033) and Badr et al., "On the structure of one-dimensional TiO2 lepidocrocite," Matter 2023 (https: / / doi.org / 10.1016 / j.matt.2022.10.015). It should be understood that the nanofilaments can be in the form of mesoporous material (e.g., powder), in the form of sheets, and in other forms. It should be understood that the nanofilaments can be tubular.

[0026] It should be understood that the nanofilaments can be in the form of a mesoporous material (eg, a powder), in the form of a sheet, or in other forms.

[0027] Aspect 2. The method of claim 1, wherein an initial concentration of the urea is in the range of 10 mmol / L to 1000 mmol / L, or wherein the initial concentration is in a concentration range of 15 mg / dL to 40 mg / dL, and wherein the final concentration is at least 10% lower than the initial concentration, and wherein the initial sample is or comprises blood or a blood product, and wherein the condition does not impair the utility of the blood or blood product for subsequent use by a human patient.

[0028] 3. The method of claim 2, wherein the final concentration is at least 30% lower than the initial concentration.

[0029] 4. The method of claim 3, wherein the final concentration is at least 50% lower than the initial concentration.

[0030] 5. The method of claim 4, wherein the final concentration is at least 70% lower than the initial concentration.

[0031] Embodiment 6. An apparatus for removing urea from an initial aqueous solution of urea, said apparatus comprising a replaceable cartridge of a metal oxide nanofilament composition through which said initial aqueous solution is directed to pass, said cartridge adapted for contacting said metal oxide nanofilaments with said initial aqueous solution of urea contained therein; the metal oxide nanofilaments optionally comprise titanium; the metal oxide nanofilaments optionally comprise carbon; and The device, wherein said oxide nanofilaments optionally have an anatase structure.

[0032] Embodiment 7. The device of claim 6, wherein the device is adapted to allow the initial aqueous solution of urea to permeate through at least a portion of the metal oxide nanofilaments.

[0033] Aspect 8. The device of claim 6, wherein the cartridge comprises a channel coated with the metal oxide nanofilaments.

[0034] Aspect 9. The device of claim 6, wherein the cartridge comprises channels coated with the metal oxide nanofilaments, the metal oxide nanofilaments comprising titanium, and the metal oxide nanofilaments having an anatase structure or a lepidocrocite structure.

[0035] 10. The device of claim 6, wherein the metal oxide nanofilament composition is present as a plurality of laminated layers.

[0036] Embodiment 11. A method comprising contacting a composition comprising metal oxide-based nanofilaments with an initial sample comprising metal ions and / or a metal under conditions such that at least a portion of said metal ions and / or said metal associate with said metal oxide nanofilaments, said metal oxide nanofilaments optionally comprising titanium, said metal oxide nanofilaments optionally having an anatase or lepidocrocite structure, and optionally irradiating said composition and said metal oxide nanofilaments and / or metal with light.

[0037] Aspect 12. The method of claim 11, wherein the metal ions and / or metals include As, Pb, Cd, Cr, Ni, Zn, Co, or Mn, Ir, Au, Ru, Re, Pt, Pd, Ag, or ions thereof.

[0038] Aspect 13. The method of claim 11, wherein the illuminating step includes xenon lamp illumination.

[0039] Aspect 14. The method of claim 11, wherein the illuminating step includes natural light.

[0040] Embodiment 15. The method of any one of claims 11 to 14, wherein the association is essentially complete within about 1 hour.

[0041] 16. The method of claim 15, wherein said association is substantially complete within about 15 minutes.

[0042] 17. The method of claim 16, wherein said association is substantially complete within about 2 minutes to about 3 minutes.

[0043] Embodiment 18. A composition comprising metal oxide nanofilaments having at least two different metal salts associated therewith. The metal of the at least two salts can be different from the metal of the metal oxide nanofilaments.

[0044] Aspect 19. The composition of claim 18, wherein at least one of the at least two different metal salts comprises nickel.

[0045] Aspect 20. The composition of claim 18, wherein at least one of the at least two different metal salts comprises iron.

[0046] Embodiment 21. A method comprising the steps of: (i) contacting a composition comprising metal oxide nanofilaments with at least one metal of a metal salt associated therewith and (ii) a solution to catalyze a reaction in said solution, wherein said metal oxide nanofilaments optionally comprise titanium, and wherein said metal oxide nanofilaments optionally have an anatase structure or a lepidocrocite structure.

[0047] Embodiment 22. The method of claim 21, wherein the reaction proceeds more rapidly than when the metal oxide nanofilaments lack at least one metal salt associated therewith.

[0048] Aspect 23. The method of any one of claims 21-22, wherein the at least one metal salt comprises iron, nickel, or any combination thereof.

[0049] Aspect 24. The method of any one of claims 21-22, wherein the solution comprises water.

[0050] Aspect 25. The method of any one of claims 21-22, wherein the reaction is an electrochemical reaction involving application of an electric current to the solution.

Claims

1. 1. A method comprising: contacting an initial sample having an initial concentration of urea in solution with a composition comprising metal oxide nanofilaments under conditions such that at least a portion of the urea adsorbs onto the metal oxide nanofilaments to produce a final concentration of urea in the solution; the metal oxide nanofilaments optionally comprise titanium; the metal oxide nanofilaments optionally comprise carbon; the metal oxide nanofilaments have a lepidocrocite structure, and and optionally further comprising irradiating said composition and said urea with light.

2. 10. The method of claim 1, wherein the initial concentration of urea is in the range of 10 mmol / L to 1000 mmol / L, or the initial concentration is in a concentration range of 15 mg / dL to 40 mg / dL, and the final concentration is at least 10% less than the initial concentration, and the initial sample is or comprises blood or a blood product, and the condition does not impair the availability of the blood or blood product for subsequent use by a human patient.

3. 3. The method of claim 2, wherein the final concentration is at least 30% lower than the initial concentration.

4. 4. The method of claim 3, wherein the final concentration is at least 50% lower than the initial concentration.

5. 5. The method of claim 4, wherein the final concentration is at least 70% lower than the initial concentration.

6. 1. An apparatus for removing urea from an initial aqueous solution of urea, said apparatus comprising a replaceable cartridge of a metal oxide nanofilament composition through which said initial aqueous solution is directed, said cartridge adapted to contact said metal oxide nanofilaments contained in said cartridge; the metal oxide nanofilaments optionally comprise titanium; the metal oxide nanofilaments optionally comprise carbon, and The device, wherein the oxide nanofilaments have a lepidocrocite structure.

7. 7. The device of claim 6, wherein the device is adapted to allow the initial aqueous solution of urea to permeate through at least a portion of the metal oxide nanofilaments.

8. The device of claim 6 , wherein the cartridge comprises a channel coated with the metal oxide nanofilaments.

9. 7. The device of claim 6, wherein the cartridge comprises a channel coated with the metal oxide nanofilaments, the metal oxide nanofilaments comprising titanium, and the metal oxide nanofilaments have a lepidocrocite structure.

10. 7. The device of claim 6, wherein the metal oxide nanofilament composition is present as multiple stacked layers.

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