Synthesis of nanoporous polyphenol-based coordination polymer frameworks and methods of using the same

Abstract

A method of synthesizing a tannic acid-coordinated Fe(III)-coordination polymer framework (TA-Fe(III)-CPF) includes coordinating tannic acid (TA) with an aqueous solution of iron(III) acetate (Fe(OAc)3) to form a mixture. The mixture is subjected to ultrasonic vibration for a predetermined time to initiate a rapid complex formation reaction. The method further includes forming the tannic acid-coordinated Fe(III)-coordination polymer framework (TA-Fe(III)-CPF) from the mixture.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 911,543, filed October 7, 2019, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates generally to the field of nanotechnology, and more particularly to systems and methods for manufacturing nanoporous polymer materials such as tannic acid-coordinated Fe(III)-coordinated polymer frameworks (TA-Fe(III)-CPF). Background Technology

[0004] Lithium is an element abundant in nature. It primarily originates from minerals and continental saltwater sources such as salt lakes and salt flats. Lithium is typically processed into lithium carbonate and lithium hydroxide. Lithium carbonate is widely used in the ceramics, glass, and pharmaceutical industries, while lithium hydroxide is mainly used by electric vehicle manufacturers. Energy storage, air treatment, glass and ceramics, and greases and lubricants are some of the major applications requiring lithium. Energy storage includes portable electronic devices, hybrid vehicles, battery electric vehicles, and power generation storage capacity.

[0005] Most lithium reserves exist in the form of ore and brine solutions. For decades, commercial lithium production has relied on ore. Extracting lithium from these ores is very expensive compared to brine solutions. Therefore, many lithium producers are turning to extraction from brine solutions. Typically, brine solutions are obtained from underground reservoirs and contain high concentrations of dissolved salts, including elements such as lithium, potassium, and sodium. Traditional methods of lithium extraction involve solar evaporation, which requires large evaporation ponds and can last for 12–24 months under suitable climatic conditions. However, this technology results in low levels of lithium recovery. Depending on the size of the well or brine pond, current methods of lithium extraction can require significant capital expenditures. Two other methods used for lithium extraction include ion exchange and solvent exchange; however, these two technologies cannot produce high-purity lithium on a large scale due to the low selectivity of lithium recovery. Therefore, there is an opportunity for improved methods to selectively extract lithium from brine solutions, resulting in high lithium recovery rates and low-cost production.

[0006] Recent advances in nanotechnology-enabled water remediation technologies are attractive for advancing traditional water purification techniques. However, the large-scale adaptability of these technologies remains a challenge due to factors such as high cost, lack of scalability, and the high risk of adverse environmental impacts. Therefore, there is an opportunity to improve fluid treatment methods through enhanced nanotechnology-enabled technologies. Summary of the Invention

[0007] This Summary is provided to introduce a selection of concepts that are further described below in the. This Summary is not intended to determine key or essential features of the claimed subject matter or the scope of the claimed subject matter. This Summary is provided to introduce a selection of concepts that are further described below in the This Summary is not intended to determine key or essential features of the claimed subject matter or the scope of the claimed subject matter.

[0008] Disclosed herein is a method of synthesizing a tannic acid-coordinated Fe(III)-coordination polymer framework (TA-Fe(III)-CPF). According to various embodiments, the method includes coordinating tannic acid (TA) with Fe(III) species to produce a mixture of coordination complexes having different coordination stoichiometries between pyrogallol units and Fe(III) units. The method further includes subjecting the mixture to ultrasonic vibrations from an ultrasonicator for a predetermined period of time to initiate a rapid complex formation reaction. The method further includes forming a tannic acid-coordinated Fe(III)-coordination polymer framework (TA-Fe(III)-CPF) from the mixture.

[0009] According to one or more embodiments, the method further includes subjecting the TA-Fe(III)-CPF to further ultrasonic vibrations; applying a centrifugal force to separate solid particles comprising the TA-Fe(III)-CPF from the mixture; and, washing the solid particles with water to produce TA-Fe(III)-CPF nanobeads having nanoporosity.

[0010] According to one or more embodiments, the cross-section of the nanobead pores is between about 5 nm and about 10 nm.

[0011] According to one or more embodiments, the cross-section of the nanobead pores is less than about 2 nm.

[0012] According to one or more embodiments, one or more steps of the method are performed at room temperature.

[0013] According to one or more embodiments, coordination bonds are formed between Fe(III) ions and hydroxyl units of pyrogallol units of tannic acid (TA) molecules, wherein the core structure of the tannic acid molecules remains intact.

[0014] According to one or more embodiments, Fe(III) ions bind to corresponding phenolic groups of tannic acid (TA) molecules after elimination of hydroxyl groups of the tannic acid (TA) molecules.

[0015] Disclosed herein are methods of synthesizing tannic acid-silsesquioxane nanoparticles (TA-NP). According to various embodiments, the methods include functionalizing a benzotriol unit within each tannic acid (TA) molecule with a silane precursor via Williamson ether synthesis by reacting the tannic acid (TA) with an alkoxysilane precursor to form sol-gel reaction sites on the TA molecule, wherein a sol-gel is formed by base-catalyzed hydrolysis and condensation of monomers into polymers dispersed in a colloidal solution. The methods also include forming integrated network sites on the periphery of the TA molecule to produce a crude product. The methods also include concentrating the crude product by placing it in a vacuum and washing the concentrated crude product with hexane to produce a refined product. The methods also include treating the refined product with deionized water to remove unreacted TA, thereby producing tannic acid-silsesquioxane nanoparticles (TA-NP).

[0016] According to one or more embodiments, the silane precursor includes an organosilane.

[0017] According to one or more embodiments, the sol-gel reaction sites are formed by alkylating hydroxyl groups of phenolic units present in the tannic acid (TA) molecule with the organosilane precursor.

[0018] According to one or more embodiments, the benzotriol hydroxyl groups of the tannic acid (TA) molecule are functionalized with the benzyl unit of the organoalkoxysilane molecule.

[0019] According to one or more embodiments, the methods further include dispersing the sol-gel in a water-based solvent to produce a coating ink; and fabricating a soft dielectric thin film of nanoparticles from the coating ink, the soft dielectric thin film including one or more of a flexible surface and an irregular surface.

[0020] According to one or more embodiments, the methods further include applying a centrifugal force to separate solid particles from the refined product; washing the solid particles with water; treating the solid particles with an ethanol solution; and collecting the TA-NP particles in solid form.

[0021] According to one or more embodiments, the carbonyl stretch of the silane molecule is lower than the ester carbonyl stretch of the tannic acid (TA) molecule.

[0022] According to one or more embodiments, the TA-silane molecule portion of the tannic acid-silsesquioxane nanoparticles (TA-NP) is thermally stable up to 425 °C.

[0023] According to one or more embodiments, the TA molecule portion of the tannic acid-silsesquioxane nanoparticles (TA-NP) is thermally stable up to 525 °C.

[0024] Disclosed herein are methods of extracting metal ions from aqueous solutions. According to various embodiments, the methods include: providing a molecular sieve coordination polymer framework (CPF) material derived from tannin or tannic acid (TA); and passing a liquid substance through the molecular sieve CPF material to extract metal ions present in the liquid substance.

[0025] According to one or more embodiments, the metal ions are extracted as TA-metal ion-silsesquioxane nanomaterials.

[0026] According to one or more embodiments, the metal ions include one or more of alkali metals, transition metals, and heavy metals.

[0027] According to one or more embodiments, the metal ions include lithium, wherein the lithium is recovered in one or more of lithium carbonate and lithium ion coordination CPFs.

[0028] According to one or more embodiments, the liquid substance includes one or more of saltwater and non-traditional water sources.

[0029] According to one or more embodiments, the molecular sieve coordination polymer framework (CPF) material includes adsorbent beads having pores with cross-sections of about less than 2 nm.

[0030] According to one or more embodiments, the molecular sieve coordination polymer framework (CPF) material includes pores, wherein the cross-section of the pores are tailored to the size of the specific metal ions to be extracted.

[0031] According to one or more embodiments, the molecular sieve coordination polymer framework (CPF) material exhibits a red-shift peak at 330 nm when viewed under a UV-Vis spectrophotometer.

[0032] According to one or more embodiments, the molecular sieve coordination polymer framework (CPF) material includes one or more of: TA-metal ion coordination composite nanomaterials, TA-Fe(III) coordination composite nanomaterials, TA-silane derivative nanomaterials, transition metal ion coordination hierarchical structure nanomaterials, and TA-silsesquioxane nanomaterials.

[0033] According to one or more embodiments, the molecular sieve coordination polymer framework (CPF) material has one or more of the forms of microparticles, nanoparticles, nanorods, nanobelts, and nanobeads.

[0034] According to one or more embodiments, the nanoporous molecular sieve coordination polymer framework (CPF) material is in one or more of the forms of filters, gaskets, membranes, adsorbent beads, packing materials, point-of-use fluorescent probes, and filter pads.

[0035] According to one or more embodiments, the method further comprises using a molecular sieve coordination polymer framework (CPF) material for one or more of multiplex detection of heavy metal ions or contaminants, selective extraction of heavy metal ions or contaminants, disinfecting water, and purifying water.

[0036] Disclosed herein are methods of extracting lithium from a brine containing lithium salts. According to various embodiments, the method comprises passing a lithium-containing brine through a filter comprising a nanoporous molecular sieve coordination polymer framework (CPF) material to extract lithium ions present in the lithium-containing brine. The method further comprises reacting the lithium ions with the nanoporous molecular sieve coordination polymer framework (CPF) material to form a lithium ion-coordinated CPF nanocomposite. The method further comprises capturing a filtrate residue after removal of the lithium ion-coordinated CPF nanocomposite.

[0037] According to one or more embodiments, the method further comprises treating the lithium ion-coordinated CPF nanocomposite with carbonic acid to produce lithium carbonate.

[0038] According to one or more embodiments, the method further comprises compacting and bagging the lithium ion-coordinated CPF nanocomposite.

[0039] According to one or more embodiments, the method further comprises passing the filtrate residue through a nanoporous coordination polymer framework (CPF) filtration material to extract or remove one or more of contaminants and heavy metal ions present in the filtrate residue.

[0040] According to one or more embodiments, the method further comprises boiling and condensing the filtrate residue to produce usable water. BRIEF DESCRIPTION OF DRAWINGS

[0041] The foregoing summary, as well as the following detailed description of preferred embodiments, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the present disclosure, exemplary embodiments are shown in the drawings; however, the present disclosure is not limited to the specific methods and instrumentalities disclosed. Example embodiments are schematically depicted in the drawings; however, the present disclosure is not limited to the specific methods and instrumentalities disclosed.

[0042] The embodiments illustrated, described and discussed herein are illustrative of the application. Since many embodiments of the application can be made without departing from the spirit and scope of the application, the present application also includes all such modifications and variations as come within the scope of the following claims and the scope of the appended claims. It is intended that the specification and figures be considered as exemplary only, with the true scope of the present application being indicated by the following claims.

[0043] Figure 1A is a graphical representation of the comparison of the UV-vis spectral traces of TA according to an embodiment of the present application, the spectral traces being taken after the addition of Fe +3 solution and after 1 hour of reaction time (taken during the reaction in water) and of the final TA-Fe(III)-CPF (spectra taken after re-dispersion in ethanol);

[0044] Figure 1B shows a graphical representation of the color of the initial TA solution (before the addition of Fe +3 and after 1 hour of reaction time according to an embodiment of the present application;

[0045] Figures 2A-2C shows scanning electron microscope (SEM) images of the morphology of the TA-Fe(III)-CPF nanobeads formed as the reaction proceeds and after sonication. Figure 2A shows SEM images of the reaction mixture taken immediately after the addition of acetic acid FE(II); Figure 2B shows SEM images of the reaction mixture taken one hour after the addition of acetic acid FE(II); and, Figure 2C shows SEM images of the reaction mixture taken after the addition of acetic acid FE(II) and subsequent sonication for one hour according to an embodiment of the present application;

[0046] Figure 3 shows transmission electron microscope (TEM) images of the nanobeads formed from the self-assembly of TA-Fe(III)-CPF according to an embodiment of the present application;

[0047] Figure 4A shows a graphical representation of the FTIR spectra of TA, TA-silane and TA-NPs; Figure 4B shows a graphical representation of the UV-vis spectra of TA, TA-silane and TA-NPs according to an embodiment of the present application;

[0048] Figures 5A-5C shows scanning electron microscope (SEM) images of TA-NP nanobeads; Figure 5D and Figure 5E shows transmission electron microscope (TEM) images of TA-NP nanobeads according to an embodiment of the present application;

[0049] Figure 6A and 6B shows scanning electron microscope (SEM) images of TA-Li(I)-CPF according to an embodiment of the present application;

[0050] Figure 7 shows a flowchart of the lithium extraction process according to an embodiment of the present application;

[0051] Figures 8A-8C Design and synthesis of various TA-CPF to achieve target structure-property functions are shown according to an embodiment of the present application;

[0052] Figure 9 Exemplary bacterial disinfection mechanism of multifunctional TA-Fe(III) CPF nanobeads in contaminated water is shown according to an embodiment of the present application;

[0053] Figure 10 Exemplary multilayer films formed by TA-Fe(III) CPFs used as fluorescent probes are shown according to an embodiment of the present application;

[0054] Figure 11 Exemplary applications of multifunctional TA-Fe(III) CPFs are shown according to an embodiment of the present application;

[0055] Figures 12A-12D Scanning electron microscope (SEM) and transmission electron microscope (TEM) images depicting the morphology of TA-Fe(III)-CPF nanobeads are shown according to an embodiment of the present application;

[0056] Figure 13A Scanning electron microscope (SEM) images of the morphology of nanofibrous TA-Fe(III)-CPF / polyacrylonitrile composites are shown; Figure 13B Scanning electron microscope (SEM) images of the morphology of TA-NP / polyacrylonitrile composites are shown; Figure 13C Images of large area nanofibrous mats are shown according to an embodiment of the present application;

[0057] Figure 14 Exemplary chemical structures and synthesis schemes of TA-Fe(III)-CPF are shown according to an embodiment of the present application;

[0058] Figure 15 Exemplary chemical structures and synthesis schemes for the preparation of tannic acid functionalized silanes are shown according to an embodiment of the present application;

[0059] Figure 16 Exemplary chemical structures and synthesis schemes for the preparation of TA-Li(I)-CPF are shown according to an embodiment of the present application. DETAILED DESCRIPTION

[0060] The following description and drawings are illustrative, and are not to be construed as limiting the disclosure. Numerous specific details are described to provide a thorough understanding of the present disclosure. However, in certain instances, well-known or conventional details are not described in order to avoid obscuring the description. References to “one embodiment” or “an embodiment” within the present disclosure can be, but not necessarily, references to the same embodiment, and such references mean at least one.

[0061] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment, nor are they necessarily mutually exclusive of other embodiments. Furthermore, the features are described as possibly being exhibited by some embodiments and not by others. Similarly, various requirements are described which can be requirements for some embodiments but not for others.

[0062] The terms used in this specification generally have their common meanings within the art, in the context of this disclosure, and in the specific context of each term’s usage. Certain terms used to describe the present disclosure will be discussed below or elsewhere in the specification to provide additional guidance to the practitioner regarding the present disclosure description. For convenience, certain terms can be highlighted, such as using italics and / or quotation marks. The use of highlighting has no influence on the scope and meaning of a term; the scope and meaning of a term are the same in the same context, whether or not it is highlighted. It should be understood that the same thing can be expressed in more than one way.

[0063] Accordingly, alternative language and synonyms can be used for any one or more of the terms discussed herein, and no special significance should be placed on whether or not a term is recited in the singular or plural, or whether a term is recited as an action, a thing, or a thing. Synonyms for certain terms are provided. Some synonyms can be used in this disclosure in various contexts depending on the application. The use of a term in the specification or claims should not be read as having an exclusive meaning; the use of “the” and / or “of the” preceding the recitation of a property, parameter, etc. should not be construed as excluding others having the recited property / parameter / etc. Likewise, the use of the terms “comprising,” “including,” “containing,” etc. should be understood such that they are open instead of closed terms. That is, the use of these terms should not be understood to exclude other elements or integers.

[0064] Without intending to limit the scope of the present disclosure, examples of instruments, apparatus, methods and related results according to embodiments of the present disclosure are given below. It should be noted that titles or sub-titles have been provided as a convenience and are not to be construed as limiting the scope of the disclosure. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the document, including definitions, will control.

[0065] Embodiments of the presently disclosed subject matter can advantageously provide efficient lithium extraction, which can selectively extract and recover high grade lithium. Embodiments of the presently disclosed subject matter can provide selective extraction of lithium from brine solutions, resulting in high lithium recovery and low cost production and conversion of lithium to lithium carbonate. Embodiments of the presently disclosed subject matter can advantageously be applied from brine solutions by entities. Embodiments of the presently disclosed subject matter can significantly reduce costs and reduce extraction time from 2 years to a few hours, resulting in low capital intensity. Oil companies and lithium producers can benefit from the embodiments described herein. Embodiments of the presently disclosed subject matter can advantageously be applied to at least the following potential markets: oil companies, lithium companies, energy storage battery manufacturing companies, oil drilling, oil refining, lithium ion battery manufacturing, electric vehicles, lithium manufacturing, and energy storage device production.

[0066] Most of the lithium reserves exist in ores and brine solutions. Commercial lithium production has previously relied on ores. It was found that extraction of lithium from these ores is very expensive compared to brine solutions. Therefore, many lithium producers are moving towards brine solutions. Brine solutions are underground reservoirs containing high concentrations of dissolved salts such as lithium, potassium, and sodium, among others. Currently, most of the lithium production uses traditional techniques such as solar evaporation, which requires large evaporation ponds, running for a period of 12-24 months under suitable climatic conditions, with high operating costs. This results in low lithium recovery. Therefore, due to the low selectivity of lithium recovery, the prior art is not sufficient for large-scale production of high purity lithium, and the current lithium extraction methods can cost thousands of dollars depending on the size of the well and / or salt pond.

[0067] Among the recent technologies for extracting lithium from brine or liquid solutions, ion exchange and solvent exchange are two relatively cost-effective technologies. However, due to the low selectivity of lithium recovery and degradation of ion exchange column materials, these two technologies are not sufficient for large-scale production of high-purity lithium. In particular, most inorganic ion exchange materials absorb lithium ions from the liquid source while releasing hydrogen ions, which facilitates the elution of lithium ions into an acidic medium and the absorption of hydrogen ions from the medium during the ion exchange process. During this process, high acidity dissolves and degrades the absorption material during the lithium elution process in acid and the lithium absorption process in the liquid source. This results in reduced performance and lifespan of the component materials. To overcome the degradation and dissolution of the material, ion exchange methods for extracting lithium with coated inorganic ion exchange materials can be used, in which the inorganic ion exchange material is protected from degradation and dissolution by introducing various polymeric coating materials on the ion exchange absorbent particles. The absorbent particles are made from a combination of various metal oxide derivatives with selected synthetic polymers as coating materials. However, one major drawback of this method is the lack of high selectivity and binding affinity in the presence of other ions due to their large pore size and low functional density of the polymer coating; this is because selectivity depends on the thickness of the coating material and the functional density of the binding sites present in the outer layer of the polymer coating.

[0068] In contrast, embodiments of the presently disclosed subject matter can help improve the selectivity of the extraction process to increase the yield of the lithium recovery process. The embodiments disclosed herein can be used for ponds of various sizes and shapes. In various embodiments disclosed herein, the high selectivity of lithium ions over other cations and anions can be achieved by tailoring the pore size of the coordination polymer framework, thereby providing fast extraction and recovery of lithium from brine and salt lakes. In one embodiment, a large-area fibrous mat-woven coordination polymer framework derived from natural tannin and transition metal ions can be used to extract lithium. The development of the coordination polymer framework (CPF) nanomaterials described herein can open new avenues for these lithium-coordinated CPF nanomaterials to be used directly as solid-state electrolytes, anode materials, and separators in solid-state lithium-ion batteries, i.e., without the need to convert the extracted product into lithium carbonate or lithium hydroxide. The embodiments disclosed herein can be advantageously applied to the lithium-ion battery, healthcare, and pharmaceutical industries. The embodiments disclosed herein can provide large-scale production of low-cost, environmentally friendly materials to extract lithium to produce high-purity lithium; this can advantageously push the lithium extraction market towards clean technologies with high lithium recovery rates and yields. Thus, the embodiments disclosed herein can provide efficient and fast metal ion extraction technologies for extracting metal ions, such as lithium ions, from sources including crude oil, brine, and wastewater, among others.

[0069] The embodiments disclosed herein can provide an efficient and fast lithium extraction technology involving novel, environmentally friendly, and low-cost molecular sieve materials with high density functionality and selectivity to lithium ions, while providing tailored nanoporosity for selective extraction of lithium ions from other metal ion contaminants. The embodiments disclosed herein can provide an innovative nanotechnology-enabled simple, fast, and low-cost lithium extraction method that includes the ability to control functionality, pore size, and selectivity at the molecular level, resulting in enhanced molecular sieve capabilities. Molecular sieve adsorbents developed using the methods described herein can be used as adsorbent beads in the nanometer range and as filtration membranes, pads, and fillers that handle high-density nanoporosity (1-2 nm pore size). According to the embodiments disclosed herein, a range of coordination polymer frameworks (CPFs) can be designed and synthesized from naturally available polyphenolic tannic acid (TA) and various transition metal ions.

[0070] The embodiments disclosed herein utilize coordination polymer frameworks (CPFs) that have molecular sieve capabilities, customizable pore sizes, and functional coordination sites, among others, that can be designed or tailored to the materials to be extracted or removed. The embodiments disclosed herein can also provide high binding affinity for selective metal ion coordination. The various embodiments disclosed herein provide the development of natural polyphenol-based CPFs, the preparation of metal-coordinated polyphenol complexes from naturally abundant tannin derivatives combined with Fe(III) salts through a fast and scalable synthesis method, Fe(III)-tannic acid CPF beads. The low-cost scalable synthesis method provided by the embodiments disclosed herein, combined with the principles of supramolecular chemistry, can advantageously provide the possibility of controlling the function and porosity of tannic acid-based CPFs at the nanoscale level for coordinating specific metal ions, including the smallest metal ions, such as lithium ions, thereby providing the extraction of lithium ions from brines and the conversion of the extracted lithium ions into pure lithium carbonate or into used lithium-coordinated CPF composites for use in, for example, lithium-ion batteries. The embodiments disclosed herein provide a fast and scalable synthesis method of synthesizing Fe(III)-tannic acid (TA) nanoporous beads and nanoporous tannic acid-silsesquioxane nanoparticles that, in some embodiments, can selectively extract alkali metal ions (Li + and Na + ) and other heavy metals from aqueous solutions.

[0071] The embodiments disclosed herein can also provide a new class of molecular sieve CPFs derived from naturally occurring and abundant polyphenol derivatives, tannins, found in plants. The embodiments disclosed herein can be used to make various products such as molecular sieves, filters, fibrous mats, and filtration membranes, which in turn are used in extraction, filtration, and / or purification processes that use these products in the form of beads or sorbents or sorbent beads, for example, for metal ion extraction and for water purification and remediation.

[0072] Various embodiments of the presently disclosed subject matter include CPFs that can contain any transition metal ion coordinated CPF hierarchies, any silane functionalized TA, and any TA silsesquioxane nanomaterial. Due to the available oxygen-rich binding sites in TA and the ability of TA to form metal ion chelating coordination networks, various embodiments of the presently disclosed subject matter can allow novel material design strategies, novel preparation processes, and self-assembly processes to fabricate hierarchies. Various embodiments of the presently disclosed subject matter can also provide prototypes of CPF-based filters, membranes, sorbent beads, and mats with high density nanoporosity. Various embodiments of the presently disclosed subject matter as described herein also include new synthetic methods to make tannic acid functionalized silsesquioxane nanoporous beads, their hierarchical microstructure and nanoparticles, and nanomaterials of tannic acid-iron(III) coordination frameworks.

[0073] Tannic acid or tannin (TA) is a naturally occurring polyphenol found in various plants and barks that can be extracted at low cost and in large scale. Due to its pyrogallol and catechol structural units, it exhibits important chemical and physical properties such as antioxidant, antibacterial, and biodegradability, making it one of the cheapest naturally abundant functional materials. Its five pyrogallol and five catechol groups provide a variety of interactive bonding sites including hydrogen bonding, ionic bonding, coordination bonding, and hydrophobic interactions; for example, TA is also rich in oxygen sites for selective lithium binding. The formation of coordination complexes with metal-phenol networks through coordination between catechol / galloyl functional groups and metal ions is beneficial to various aspects of the presently disclosed subject matter. A wide variety of tannic acid-metal coordination complexes have been applied as thin films or particles with tailored properties or in the formation of new metalogels. The use of TA as a pore-forming agent or additive ingredient in materials science has attracted attention because it is not only inexpensive, environmentally friendly, non-toxic, but also a non-surfactant template. For example, TA can be used as a pore-forming agent to tune the porosity of other inorganic particles to make mesoporous materials with tunable mesopores in the size range of 6 to 13 nm. As another example, dopamine-functionalized tannic acid templated mesoporous silica nanoparticles can be used as sorbent materials for efficient removal of copper(II) ions from aqueous solutions.

[0074] The embodiments disclosed herein can include various products and applications, including the following: (1) Fe(III)-tannic acid CPF nanostructured nanoporous beads, composition and preparation; (2) tannic acid-silsesquioxane CPF nanostructures, composition and preparation; (3) lithium-coordinated tannic acid CPF nanostructures, composition and preparation; (4) extraction of lithium ions from seawater / brine, produced water using naturally abundant polyphenol-based CPFs (broad definition), not limited to tannic acid-based metal coordination frameworks and their silsesquioxane nanostructures, gels, aerogels and sols, but including all polyphenol-based CPFs and their silsesquioxane derivatives; (5) polyphenol-based CPFs that are potentially useful for water purification, heavy metal extraction, extraction of lithium ions from seawater and other crude waste waters (including brines) and mining ponds; and (6) alkali metal ion (Li + and Na + ) coordinated CPF nanostructures, composites and their derivatives for potential applications in lithium ion batteries and energy storage.

[0075] The embodiments disclosed herein include, among others: (1) hierarchical structures of various TA-metal ion coordination complexes, such as TA-Fe(III) coordination complexes; (2) TA-silane derivatives that functionalize the hydroxyl groups of the triphenol units in TA with various alkoxysilanes; (3) TA-silsesquioxane nanoparticles, microparticles, nanorods, nanobelts with different functionalities, sizes and porosities; and (4) nanomaterials, hierarchical structures, microparticles, beads prepared from combinations of unmodified TA, TA-Fe(III) coordination complexes and TA silanes. Some embodiments examples and their chemical structures are shown in the figures. According to various embodiments of the presently disclosed subject matter, the material design and preparation phase can include design strategies, precursor preparation and adsorbent bead preparation on TA-metal ion coordination polymer frameworks.

[0076] Various embodiments of the presently disclosed subject matter use TA as a core material to produce novel hierarchical coordination frameworks (CPF) for metal ion extraction, particularly lithium from lithium sources, and remediation of water and removal of heavy metal ions from non-traditional water sources. The inventors’ preliminary studies involve the synthesis of a series of novel nanomaterials derived from tannic acid-based coordination polymer frameworks. The description herein demonstrates the preparation, characterization, optical properties and particle morphology of nanomaterials formed from self-assembly of TA-Fe(III) coordination complexes and base-catalyzed sol-gel polymerization of tannic acid-functionalized silanes, for example as shown in Scheme 1 of Figure 14 .

[0077] The synthesis, characterization, and morphology of TA-Fe(III)-CPF nanobeads according to at least one embodiment include the development of a simple and rapid synthetic method for fabricating highly porous nanobeads of TA-coordinated Fe(III)-coordinated polymer frameworks (TA-Fe(III)-CPF). The nanobeads are prepared by coordinating TA with ferric acetate (Fe(OAc)3) in water followed by sonication. Scheme 1 describes the chemical reaction for preparing TA-Fe(III)CPF (…). Figure 14 Scheme 1) is shown, along with the space-filled structure of the geometry-optimized tannic acid (TA) structure and the structure of the iron coordination complex. The inventors have developed a simple and rapid synthetic method for the first time to produce highly porous TA-Fe(III)-CPF nanobeads.

[0078] Therefore, TA-Fe(III)-CPF nanoporous beads were prepared in water at room temperature using a simple and rapid complexation reaction. Figure 1A As shown, the formation of the complex was monitored by collecting UV-vis spectra before and after the addition of the iron solution, and after a one-hour reaction time. In the initial study, the inventors noted that within one hour, the reaction mixture changed from a clear solution to a light purple color, and eventually to a dark purple suspension (see [link to study].) Figure 1B ).

[0079] The UV-vis trace confirmed the reaction process and the formation of the metal coordination complex. The spectrum exhibited a broad redshift at 330 nm and a well-resolved vibrational absorption maximum at 218 nm for the pyrogallol moiety lacking TA (see [reference needed]). Figure 1A TA-Fe(III)-CPF nanobeads were collected after sonication for 1 hour, followed by centrifugation and repeated washing with water. The nanobeads prepared in this manner were fully characterized by powder X-ray diffraction, XPS, FTIR, and UV-Vis spectroscopy. In the initial analysis, FTIR spectral traces confirmed the formation of coordination bonds between Fe(III) and the hydroxyl groups of the pyrogallol moiety, while maintaining the integrity of the tannic acid core structure. At 3300 cm⁻¹... -1 The reduction in hydroxyl stretching further proves that Fe +3 It was successfully bound to the phenolic group of tannic acid.

[0080] The nanobeads prepared in this manner were thoroughly characterized using techniques including powder X-ray diffraction, XPS, FTIR (Fourier transform infrared spectroscopy), and UV-Vis spectroscopy. The FTIR spectral traces confirmed the formation of coordination bonds between Fe(III) and the hydroxyl groups of the pyrogallol moiety, while maintaining the integrity of the core structure of the tannic acid (TA) molecule. At 3300 cm⁻¹... -1 The reduction in hydroxyl stretching further proves that Fe +3The ions successfully bind to the TA phenolic complex by eliminating the hydroxyl groups of tannic acid (TA).

[0081] After the extraction of the synthetic tannic acid-coordinated Fe(III)-coordinated polymeric framework in the form of beads (TA-Fe(III)-CPF), the surface morphology of the beads, their nanoporosity and the particle crystallinity were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques combined with dark field selected area diffraction mode (SAED) techniques, as shown in Figures 2A-2C Additionally, the formation of the nanobeads and their morphological changes were investigated as the reaction was proceeding by taking small aliquots from the reaction mixture and then drop-casting them on a silicon substrate for SEM analysis. The sample prepared immediately after the addition of the iron solution showed aggregated nanoparticles with a particle size ranging from 50 nm to 200 nm. The particles formed after one hour of the addition of the iron solution were larger in size compared to the nanoparticles formed in the initial stage. The particles collected after the sonication step showed the same or similar morphology to the nanoparticles formed in the initial stage and after one hour of reaction time. The transmission electron microscopy image taken at the moment after the one hour reaction interval, followed by the sonication and re-dispersion in ethanol, showed larger nanopores (pore size ranging from 5 nm to 10 nm) and smaller nanopores of uniform size (<2 nm), as shown in Figure 3 The self-assembled nanocrystals of the iron-coordinated hydroxylated (Fe +3 -O) sites in the beads were clearly visible and supported the presence of the coordinated iron on the hydroxyl units of the pyrogallol units.

[0082] The surface morphology of the beads manufactured by the method disclosed herein and their nanoporosity were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and are shown in Figure 12. The formation of the nanobeads and their morphological changes were investigated as the reaction was proceeding by taking small aliquots from the reaction and then drop-casting them on a silicon substrate for SEM analysis. The sample prepared immediately after the addition of the iron solution showed aggregated nanoparticles with a particle size ranging from 50 nm to 200 nm. The particles formed after one hour were larger in size compared to the nanoparticles formed in the initial stage. The particles collected after the sonication step exhibited the same morphology to the nanoparticles formed in the initial stage and after one hour of reaction time. The transmission electron microscopy image taken after one hour of the reaction (followed by the sonication and re-dispersion in ethanol) showed larger nanopores (pore size ranging from 5 nm to 10 nm) and smaller nanopores of uniform size (<2 nm), as shown in Figure 12D The self-assembled nanocrystals of the beads were clearly visible. XPS and Raman spectroscopy identified the iron-coordinated hydroxylated (Fe +3formation of an -O) linkage and confirmed the successful formation of a complex with the pyrogallol unit in tannic acid. The method described herein can be used to prepare Fe(III)-TACPF on a large scale, to produce molecular sieves for water remediation and point-of-use sensors for detecting microbial contaminants at a low cost.

[0083] The inventors observed that functionalizing the pyrogallol unit of tannic acid with silane precursors introduces sol-gel reaction sites at the periphery of tannic acid. The sol-gel polymerization follows a hydrolysis and condensation process in the presence of a base to produce a sol of nanoparticles with a silsesquioxane core. These colloidal sols can also be dispersed in water-based solvents to produce inks that can be coated on any flexible and irregular surface using simple self-assembly driven spray techniques.

[0084] As shown in Scheme 2 (see Figure 15 ), using Williamson ether synthesis, sol-gel reaction sites were introduced randomly onto the tannic acid backbone upon alkylation of the hydroxyl groups of the phenolic units with organosilane precursors. The crude TA-silane prepared in this way was concentrated under vacuum and further purified by washing with hexane followed by washing with deionized water to remove unreacted tannic acid and other products. Although there was a tendency to hydrolyze the methoxy groups of the silane units during washing with deionized water, FTIR analysis showed no apparent hydroxyl broad IR (infrared) stretch at 3000-3500 cm -1 (figure 4(a)). The FTIR spectrum of TA-silane ( Figure 4A ) confirmed the presence of characteristic bands of Si-O (1120-1025 cm -1 ) and Si-C (1207 cm -1 ). Ester carbonyl and aromatic C-C (carbon-carbon) stretching vibrations were observed at 1692 cm -1 and 1602-1511 cm -1 , respectively. The carbonyl stretch of the silane was lower than that of the tannic acid ester. UV-vis absorption spectra were collected in ethanol and compared with that of TA. In general, the absorption spectrum of tannic acid exhibits two absorption maxima at 212 nm and 277 nm with a weak shoulder at 240 nm. In comparison with the TA absorption, the maximum absorption at 212 nm was missing in the TA-silane absorption spectrum and showed an enhanced absorption at 246 nm, which was slightly red-shifted to the shoulder of TA at 240 nm. The original TA absorption at 277 nm was less pronounced. The additional absorption peak at 344 nm in TA-silane confirmed the functionalization of the pyrogallol hydroxyl groups with the benzyl units of the organoalkoxysilane.

[0085] Figure 1A was just before the addition of Fe +3Figure showing the comparison of UV-vis spectra traces of TA and final TA-Fe(III)-CPF after solution and after 1 hour reaction time (spectra taken during reaction in water). (Spectra taken after re-dispersion in ethanol). Figure 1B Figure showing the color of the initial TA solution (Fe +3 added) and after 1 hour reaction time. Figure 2 represents the scanning electron microscopy image of the nanoporous beads of Fe(III)-tannic acid CPF. Figure 3 Figure representing the transmission electron microscopy image of the nanoporous beads of Fe(III)-tannic acid CPF. Figure 4A Figure showing the FTIR spectra of TA, TA-silane and TA-NP; Figure 4B Figure showing the UV-vis spectra of TA, TA-silane and TA-NP. Figure 5 represents the transmission electron microscopy image of the nanoporous beads of Fe(III)-tannic acid CPF. Figure 6 represents the scanning electron microscopy image of the self-assembled nanoporous microstructure of Li + coordinated tannic acid CPF. Figure 7 Figure representing a flow chart illustrating the lithium ion extraction process according to one aspect of the application. Figure 8 shows the material design approach to achieve targeted structure-property function. Figure 9 Figure showing the mechanism of bacterial disinfection of multifunctional TA-Fe(III) CPF nanobeads in contaminated water. Figure 10 Figure showing the multiple membranes as fluorescent probes. Figure 11 Figure showing the research overview of water treatment using CPF. Figure 12A and 12B Figure showing the morphology of TA-Fe(III)-CPF nanobeads. Figure 13A Figure showing the nanofibers of TA-Fe(III)-CPF / polyacrylonitrile composites; Figure 13B Figure showing the nanofibers of TA-NP / polyacrylonitrile composites; Figure 13C Figure showing the image of large area nanofiber mat. Figure 14 Figure showing Scheme 1, which represents the chemical reactions for the preparation of TA-Fe(III) CPF described in the first scheme. Figure 15 Figure showing Scheme 2, which represents the chemical reactions for the preparation of tannic acid-silane and its possible chemical structure. Figure 16 Figure showing Scheme 3, which represents the preparation of Li coordinated tannic acid complex and possible chemical structure.

[0086] The methods described herein demonstrate the use of improved Methods, feasibility of tannic acid silsesquioxane nanoparticles (TA-NPs) from TA-silane. TA-NPs are prepared from direct hydrolysis and condensation of TA-silane without silica sol as nucleation seeds. In a typical procedure of direct hydrolysis and condensation of TA-silane without silica seeds, spherical TA-NPs are obtained by adjusting the base concentration relative to the TA-silane precursor. A series of controlled experiments are currently being conducted to adjust the reaction parameters, such as base concentration, solvent volume, and reaction time. After a 24-hour reaction time, the particles are collected in the form of off-white solids by centrifugation and washed repeatedly with water and 70% ethanol, in that order. The particles prepared in this way show a broad size distribution, with an average size ranging from 50 nm to 400 nm. As shown in FIG. 5, the particles are spherical, showing uniformly distributed nanopores. The effect of base concentration on particle formation, their size distribution, and particle morphology will be investigated in ethanol solutions at a fixed silane concentration. Our preliminary results support the proof-of-concept of the fabrication of nanoporous TA-silsesquioxane nanoparticles by the base-catalyzed sol-gel polymerization method. This new synthesis route offers a way to fabricate functional molecular sieves with multiple capabilities for extraction, heavy metal removal, and water remediation technologies.

[0087] Accordingly, in accordance with at least one embodiment, the synthesis, characterization, and morphology of tannic acid-silsesquioxane nanoparticles (TA-NPs) can include functionalization of the pyrogallol units of tannic acid (TA) with silane precursors to introduce sol-gel reaction sites at the periphery of tannic acid. Sol-gel polymerization follows a hydrolysis and condensation process in the presence of a base. This results in the production of nanoparticulate sols with a silsesquioxane core structure. In various embodiments, these sols can be dispersed in water-based solvents to produce coating inks for the fabrication of nanoparticulate soft dielectric thin films on any flexible and irregular surfaces using, for example, various simple self-assembly driven spray techniques.

[0088] According to at least one embodiment, a method of synthesizing a tannic acid-coordinated Fe(III)-coordination polymer framework (TA-Fe(III)-CPF) includes coordinating tannic acid (TA) with an aqueous solution of iron(III) acetate (Fe(OAc)3) to form a mixture. The method also includes subjecting the mixture to ultrasonic vibrations of an ultrasonicator, for example, for a predetermined period of time, to initiate a rapid complex formation reaction. In some embodiments, other sources of ultrasonic vibrations can be used in addition to an ultrasonicator to produce the ultrasonic vibrations. The method also includes forming the tannic acid-coordinated Fe(III)-coordination polymer framework (TA-Fe(III)-CPF) from the mixture. According to one or more embodiments, one or more steps of the method are performed at room temperature.

[0089] According to another embodiment, a method of synthesizing tannic acid-silsesquioxane nanoparticles (TA-NPs) includes functionalizing the pyrogallol units within each tannic acid (TA) molecule with a silane precursor by direct hydrolysis to form sol-gel reaction sites on the TA molecule, where a sol-gel is formed by the conversion of monomers into polymers dispersed in a colloidal solution. The method also includes forming integrated network sites on the periphery of the TA molecule to produce a crude product. The method also includes concentrating the crude product by subjecting the crude product to a vacuum, and washing the concentrated crude product with, for example, hexane, to produce a refined product; other suitable chemicals can also be used to wash the concentrated crude product. The method also includes treating the refined product with deionized water, for example, to remove unreacted TA, to produce tannic acid-silsesquioxane nanoparticles (TA-NPs). According to one or more embodiments, one or more steps of the method are performed at room temperature.

[0090] According to one embodiment, a method of extracting metal ions from an aqueous solution includes providing a molecular sieve coordination polymer framework (CPF) material derived from tannin or tannic acid (TA), and passing a liquid substance through the molecular sieve CPF material to extract metal ions present in the liquid substance. According to one or more embodiments, one or more steps of the method are performed at room temperature.

[0091] According to one embodiment, a method of extracting lithium from a lithium-containing brine includes passing the lithium-containing brine through a filter comprising a nanoporous molecular sieve coordination polymer framework (CPF) material to extract lithium ions present in the lithium-containing brine. The method can also include reacting the lithium ions with the nanoporous molecular sieve coordination polymer framework (CPF) material to form a lithium ion-coordinated CPF nanocomposite. The method can also include capturing a filtrate residue after removing the lithium ion-coordinated CPF nanocomposite. According to one or more embodiments, one or more steps of the method are performed at room temperature.

[0092] According to at least one embodiment, as described in Scheme 2 (see Figure 15 ) sol-gel reaction sites are randomly introduced onto the tannic acid (TA) backbone when alkylating the hydroxyl groups of the phenolic units of the TA molecule with an organosilane precursor using the Williamson ether synthesis method to produce TA-silane precursors.

[0093] As is well known to those skilled in the art, Williamson ether synthesis is an organic reaction that involves the formation of an ether from an organic halide and a deprotonated alcohol (alkoxide). This reaction was introduced by Alexander Williamson in 1850. Typically, it involves an alkoxide with a primary alkyl halide via an S N2Reaction of the reaction. The Williamson reaction is very versatile and is widely used in laboratory and industrial synthesis and remains the simplest and most popular method for the preparation of ethers. Both symmetrical and asymmetrical ethers are readily prepared. In particular, the intramolecular reaction of a halohydrin to an epoxide. In the case of an asymmetrical ether, there are two options for the reactants, based on availability or reactivity, and usually one is preferred. The Williamson reaction is also often used to prepare ethers indirectly from two alcohols. One of the alcohols is first converted to a leaving group (usually a tosylate), and then both are reacted together. The alkylating agent (or phenoxide) can be a primary, secondary, or tertiary alcoholate. On the other hand, the alkylating agent is most preferably a primary alcoholate. Secondary alkylating agents can also react, but tertiary alkylating agents are usually too prone to side reactions to be useful. The leaving group is usually a halide or sulfonate ester that is synthesized for the purpose of the reaction. Because the conditions of the reaction are rather harsh, protecting groups are often used to stabilize other parts of the reaction molecule (e.g., other alcohols, amines, etc.).

[0094] According to at least one embodiment, the crude product concentrated under vacuum is further purified by washing with hexane followed by washing with deionized water to remove unreacted tannic acid (TA) and other products. Although there is a tendency to hydrolyze the methoxy stretch of the silane units during washing with deionized water, FTIR analysis shows no significant hydroxyl broad IR (infrared) stretch at 3000 cm -1 to 3500 cm -1 -1 (Figure 4(a)). The FTIR spectrum of TA-silane (Figure 4(b)) also confirms the presence of characteristic bands of Si-0 (1120-1025 cm Figure 4A ) and Si-C (1207 cm -1 ). The characteristic bands of Si-0 and Si-C are also observed in the FTIR spectrum of TA-silane (Figure 4(b)) at 1120 cm -1 and 1207 cm -1 -1, respectively. The characteristic bands of Si-0 and Si-C are also observed in the FTIR spectrum of TA-silane (Figure 4(b)) at 1120 cm -1 and 1207 cm -1The ester carbonyl and aromatic C-C (carbon-carbon) stretching vibrations were observed at 1720 and 1600 cm"1, respectively. The carbonyl stretch of the silane was found to be lower than the ester carbonyl stretch of the tannic acid (TA). This further confirms the silane functionalization. TGA analysis showed that TA-silane is thermally stable up to 425 °C with an initial mass loss of ~ 15% at 400 °C, while TA is thermally stable up to 525 °C with an initial mass loss of ~ 15% at 400 °C. In both cases, the initial mass loss can be due to trace amounts of impurities, including oligomeric fractions and solvent molecules. However, the decomposition temperature of TA-silane is lowered by ~ 100 °C, which reflects the lower thermal stability of TA-silane relative to that of TA. The unfunctionalized TA shows a total organic mass loss of 96% at 600 °C, while TA-silane shows a total organic mass loss of 83% at 475 °C. The decrease in mass loss is due to the decomposition of the total organic content compared to its original polymer, while the higher residual weight is due to the inorganic content of TA-silane; these observations further indicate the incorporation of silane units onto the polymer backbone.

[0095] According to at least one embodiment, the UV-vis absorption spectra were collected in ethanol and compared to that of TA. Typically, the absorption spectrum of tannic acid (TA) exhibits two maxima at 212 nm and 277 nm with a weak shoulder at 240 nm. When compared to the TA absorption, the maximum absorption at 212 nm is missing in the absorption spectrum of TA-silane and shows an enhanced absorption at 246 nm, which is slightly red-shifted to the shoulder of TA at 240 nm. It is noted that the original TA absorption at 277 nm is less pronounced. The additional absorption peak at 344 nm in TA-silane confirms the functionalization of the pyrogallol hydroxyl groups by the benzyl units of the organoalkoxysilane.

[0096] According to at least one embodiment, the improved Tannic acid silsesquioxane nanoparticles (TA-NPs) were synthesized from TA-silane by the method. Thus, TA-NPs can be synthesized from the direct hydrolysis and condensation of TA-silane without the need for nucleation seeds of silica sol. In the typical process of direct hydrolysis and condensation of Q-silanes without silica seeds, spherical TA-NPs were obtained by adjusting the base concentration relative to the TA-silane precursor. A series of controlled experiments can be performed to adjust the reaction parameters, such as base concentration, solvent volume, and reaction time. After 24 hours of reaction, the off-white solid particles were collected by centrifugation. The resulting solid material was washed repeatedly with water and then with 70% ethanol. According to at least one embodiment, the particles prepared in this way showed a broad size distribution with an average size ranging from 50 nm to 400 nm. As Figures 5A-5EAs shown, the particles are spherical, showing a uniform distribution of nanopores. The effect of base concentration on particle formation, their size distribution, and particle morphology can be investigated in ethanol solutions of fixed silane concentration.

[0097] Embodiments of the presently disclosed subject matter can also be used for low-cost wastewater treatment and reuse processes. Embodiments of the presently disclosed subject matter can utilize the novel hierarchical microstructure of natural polyphenol-based coordination polymer frameworks (CPF) to provide innovative nanotechnology-enabled simple, fast, and low-cost wastewater treatment and reuse processes. The ability of CPFs to control functionality, pore size, and selectivity at the molecular level can enable the utility and versatility of CPFs as molecular sieves for fast and effective water purification and reuse of produced water from non-traditional water sources. CPFs can be used to develop nanoporous sorbents, liners, membranes, filter pads, and in situ fluorescence probes for multiplexed detection of heavy metal ions and pollutants for selective extraction and removal in a fast and simple manner as well as water disinfection and decontamination. Embodiments of the presently disclosed subject matter can help provide efficient and cost-effective services to wastewater treatment plants, water purification departments, produced water handlers, and transporters. Since various embodiments of the presently disclosed subject matter can utilize high-value-added, environmentally friendly nanomaterials based on agricultural and forest-derived products, water treatment and reuse processes including the presently disclosed subject matter can overcome the high cost, scalability challenges, and potential environmental and health risks associated with current nanobased water purification nanomaterials.

[0098] The demand for freshwater is growing exponentially, particularly for food production, as 70% of the world's freshwater withdrawal is already used for agricultural irrigation. Current technologies are reaching their limits in meeting increasingly stringent water quality standards and treating emerging pollutants such as pharmaceuticals, personal care products, and viruses. The design of existing wastewater collection and water supply systems cannot meet the growing demand. Centralized treatment and distribution systems have little flexibility in responding to water quality or quantity demands and are no longer a solution for sustainable urban water supply. It is projected that the population will grow to 3 billion by 2025, and the rapid growth of the population will leave 700 million people living below the 1700 cubic meter per capita per year threshold of water stress. With cost, scalability, environmental safety, and clean water as key drivers to advance future water treatment and quality control technologies, it is necessary to develop low-cost, environmentally friendly, and safe, innovative nanobased water treatment technologies.

[0099] Embodiments of the presently disclosed subject matter can provide nanotechnology-enabled water remediation technologies. The application of the highly advanced nanotechnologies described herein to traditional engineering processes can advantageously provide new opportunities for the technological development of advanced water and wastewater technology processes. The nanoscale engineered materials described herein can provide great potential for water purification, treatment, and reuse technologies, particularly for decentralized treatment systems, point-of-use devices, and severely degradable pollutants.

[0100] The exceptional properties of nanomaterials, such as high surface area, photosensitivity, catalytic and antimicrobial activity, electrochemical, optical and magnetic properties, as well as tunable pore size and surface chemistry, provide useful characteristics for water treatment applications. Applications of various embodiments of the disclosed subject matter can also include sensors for water quality monitoring, adsorbents, high-performance membranes, and disinfection and purification processes that can collect solar energy in parallel. The modular, multifunctional, and efficient processes permitted by nanotechnology can provide pathways to retrofitting aging infrastructure and developing high-performance, low-maintenance decentralized treatment systems (including point-of-use devices). One of the most significant advantages of the nanomaterials disclosed herein compared to conventional water treatment technologies is their ability to integrate various properties to form multifunctional systems, such as nanocomposite membranes, capable of both retaining particles and removing contaminants. Nanomaterials fabricated using the methods disclosed herein can advantageously allow for higher process efficiencies due to their high-density functionality and higher surface area.

[0101] Nanomaterials for various water remediation processes have been demonstrated in the laboratory stage. For example, carbon nanotubes (CNTs) can be used as nano-adsorbents (as an alternative to activated carbon) because they can effectively remove organic and metallic contaminants. The availability of binding sites and non-covalent interactions between contaminants and CNTs allows for the control of organic contaminant adsorption on CNTs. Binding sites on carbon nanotubes are more readily available than those on activated carbon, which contains impenetrable pores, especially for macromolecules such as tetracycline. The π-electron-rich surface of CNTs can act as an electron donor or acceptor for many polar aromatic compounds, such as nitroaromatics and phenols. While hydrophobic graphite surfaces are the primary sites for organic adsorption, metal ions are primarily adsorbed onto surface functional groups, which can be reversed by adjusting the pH, enabling reuse. The fibrous structure, antimicrobial activity, and conductivity of CNTs make them suitable for use in antimicrobial filters. The antimicrobial mechanism of CNTs and some other carbon-based nanomaterials is thought to involve membrane perturbations and electron structure-dependent oxidative stress. Short, dispersed, small-diameter metallic carbon nanotubes are more toxic. CNT filters manufactured using the methods described herein can also be used in electrochemical processes, where small intermittent voltages inactivate physically trapped microorganisms through oxidation. The potential causes viruses to electrophore to CNTs, mitigating the negative impact of natural organic matter on virus retention by the CNT filter. Fullerenes and CNTs are also photosensitive and can generate reactive oxygen species in water. When activated by visible light, aminofullerenes and fullerols produce singlet oxygen (…). 1 O2 (oxygen-rich oxygen) exhibits high selectivity for pollutants containing electron-rich moieties, enabling them to degrade in water with less interference from background organic matter (such as wastewater). However, the high cost of CNTs limits the commercial application of CNT technology.

[0102] Nanomagnetic materials have unique superparamagnetic properties that allow for the separation of heavy metals from water in a weak magnetic field. This magnetic property can allow for a new class of core-shell structured nanoparticles, where the shell provides the desired functionality, while the magnetic core makes the particles easy to separate. Core-shell nanomaterials can be composed of a shell chemically suitable for fast, selective adsorption and a reactive core for degrading the adsorbed pollutants. Specialized nanoadsorbents are also designed using dendrimers with specific binding sites. Advances in sensor development have demonstrated that the effective integration of nanomaterials and recognition agents (e.g., antibodies, aptamers, carbohydrates, and antimicrobial peptides) can yield fast, sensitive, and selective sensors for microbial detection. Nanomaterials can also be used to improve sensor sensitivity and speed and enable multiplexed target detection due to their unique electrochemical, optical, or magnetic properties. For example, magnetic nanoparticles and CNTs can be used for sample concentration and purification. Quantum dots (QDs), dye-doped nanoparticles, noble metal nanoparticles, and CNTs are widely used in nanosensor research. QDs have a broad absorption band, but a narrow and stable fluorescence emission spectrum that varies with particle size and chemical composition, allowing for multiplexed target detection with one excitation source. Dye-doped silica and polymer nanoparticles exhibit high luminescence intensity because a large number of dye molecules are confined in each nanoparticle. Noble metal nanomaterials also improve surface-enhanced Raman spectroscopy, enabling enhancement factors up to 10-fold and single-molecule detection. CNTs are excellent materials for electrodes and field-effect transistors. Some nanomaterials have strong antimicrobial properties, including nano-Ag, nano-ZnO, nano-TiO2, nano-Ce2O4, CNTs, and fullerenes. These nanomaterials inactivate microorganisms by releasing toxic metal ions (e.g., Ag + and Zn 2+ ), damaging cell membrane integrity upon direct contact (e.g., CNTs, nC60, nano-Ce2O4), or producing reactive oxygen species (e.g., nano-TiO2, fullerenols, and amino fullerenes), with less tendency to form disinfection byproducts. Among them, nano-Ag is a common choice for point-of-use water treatment devices due to its strong and broad-spectrum antimicrobial activity and low toxicity to humans.

[0103] Accordingly, the embodiments described herein provide for the manufacture of novel tannic acid-based coordination polymer frameworks (CPF) for water purification and remediation applications. The described embodiments can provide for high nanoporous filters, pads, and membranes using tannic acid-based CPFs for water purification and remediation. Utilizing tannic acid (TA) as a core material, the embodiments described herein can provide a series of novel tannic acid-iron coordination complex nanomaterials, TA-Fe(III)-CPF, and tannic acid silsesquioxane nanoparticles, TA-NP.

[0104] Coordination polymer frameworks (CPFs) offer highly porous and high density functionalities for rational design of high surface area platforms with selective and tailored pore environments for use as molecular sieves. Coordination polymers (CPs) and their subclass metal-organic frameworks (MOFs) are highly porous self-assembled nanostructures with high surface area and defined pore size. CPFs are linked by coordination bonds to functional organic ligands, precisely positioning the metal building blocks. In contrast to traditional porous solids such as zeolites, activated carbons, and mesoporous silicas, CPFs allow for the design of framework structures and tailored pore environments at the molecular level. Their size, shape, and self-assembly can be carefully controlled through efficient covalent synthetic methods to produce three-dimensional (3-D) hierarchical structures. These nanoscale building blocks and their assemblies combine the flexibility, functionality, transparency, and ease of processing of soft matter (organics) with the electrical, thermal, and mechanical properties of hard matter (inorganics). Thus, CPFs offer a new window for fine-tuning structural nodes with known geometric configurations and coordination environments. Their porous structure, as well as the geometric arrangement of inorganic and organic components, enables the rational design of high surface area platforms.

[0105] The application of CPFs as adsorbents for water remediation has been scarce so far, mainly due to the poor stability of currently synthesized MOFs in aqueous media. With the implementation of synthetic strategies to manufacture water-stable MOFs, the number of MOFs shown in water remediation is mainly limited to six high-cost representative MOFs - MIL-53 (Fe), MIL-101 (Fe), UIO-66 (Zr), IRMOF-3 (Zn), MOF-5 (Zn), and ZIF-8 (Zn), for which large-scale production is not practical. Therefore, for potential applications in this field, it is necessary to develop a new series of water-stable CPFs at a large scale and low cost.

[0106] The improved sol-gel method described herein facilitates the production of biodegradable, non-toxic, environmentally friendly nanoporous nanoparticles with a silsesquioxane core structure. Thus, the importance of the presently disclosed subject matter's embodiments can open new perspectives in the synthetic progress for producing functional nanoporous, natural polyphenol-based molecular sieves derived from agricultural and forest-derived products.

[0107] The inventors have explored the use of a new class of coordination polymer frameworks that are naturally abundant and environmentally friendly for water treatment technologies. According to various embodiments of the presently disclosed subject matter, a new class of coordination polymer frameworks (CPF) using natural polyphenols, tannic acid (TA) are designed, synthesized and explored for nanotechnology-enabled wastewater treatment and reuse processes. Due to the oxygen-rich binding sites of tannic acid and its ability to form metal ion chelating coordination networks, the inventors’ research has focused on new material design strategies, their preparation, self-assembly processes to fabricate hierarchical CPFs, and their use as nanofilters, nanomembranes, nanoadsorbents, and nanomatrices. The introduction of sol-gel reaction sites on the polyphenol backbone, resulting in silsesquioxane frameworks, provides additional material stability, porosity, and selectivity functionalities to the coordination polymer frameworks of tannic acid. These hierarchical microstructures have molecular sieving capabilities, customizable pore sizes, and functional coordination sites that provide high binding affinity for organic and inorganic pollutants and microorganisms.

[0108] According to at least one embodiment, natural polyphenol-based CPFs are synthesized by a fast and scalable synthesis method, developed to fabricate metal-coordinated tannic acid complexes, Fe(III)-TA CPFs, nanoporous beads. This low-cost, scalable synthesis method, combined with principles of supramolecular chemistry, exhibits the possibility of manipulating the functionality and porosity of tannic acid-based CPFs at the nanoscale to coordinate specific metal ions, including the smallest metal ion (lithium ion), providing the possibility of extracting lithium ions from brine and converting into pure lithium carbonate or lithium-coordinated CPF composites for lithium-ion batteries. Thus, in some embodiments, lithium recovery is as lithium carbonate and / or lithium-ion coordinated CPFs. Embodiments described herein provide a new class of molecular sieving CPFs derived from naturally abundant tannic acid present in plants.

[0109] Embodiments of the presently disclosed subject matter can advantageously provide: (1) reduced use of freshwater and increased resilience / sustainability of agriculture through innovative methods, tools, and technologies that allow irrigation with non-traditional water resources; (2) new uses and high-value products from nanobiomaterials from agriculture and forests for food and non-food applications; (3) nanotechnology-enabled smart sensors for accurate, reliable, and cost-effective early and rapid detection of pollutants in water; and (4) discovery and characterization of nanoscale phenomena, processes, and structures that are relevant and important to agriculture and food.

[0110] Various embodiments of the presently disclosed subject matter can also provide: (1) discovery and characterization of nanoscale structures based on natural polyphenols; (2) development of nanobased simple, fast, and low-cost wastewater treatment and reuse systems; and (3) fabrication of portable, field-deployable, and agriculturally affordable sensors for water quality monitoring, pollutant detection, and disinfection.

[0111] The currently disclosed embodiments of the subject matter also offer potential environmentally friendly and low-cost nano-based technologies for advancing wastewater treatment, reuse, and the use of point sensors. Furthermore, the currently disclosed embodiments of the subject matter can maintain agricultural resilience by reducing freshwater demand, improving water quality, affordability, and safety, while simultaneously increasing the protection of natural resources, the environment, and agro-ecosystems. The currently disclosed embodiments of the subject matter can be advantageously applied to the manufacture of the novel coordination polymer frameworks disclosed herein, in the form of molecular sieves, filters, membranes, and sensing materials for developing water treatment technologies.

[0112] According to various implementation schemes, based on the synthesis of coordination polymer frameworks (CPFs) and metal-organic frameworks (MOFs), it is possible to prepare various transition metal ions (Fe2+, Fe2+, Fe3 ... +3 Zn +2 and Ni +2 Coordinated TA-CPF and multifunctional TA-based silsesquioxane nanoparticles (TA-NPs) with customized pore sizes and particle diameters. Developing novel high-value biodegradable nanomaterials will establish structure-property relationships, enabling the introduction of external porosity into the polyphenol framework and silsesquioxane core structure, providing high-density functionality for contaminant removal and disinfection.

[0113] TA-CPF is suitable as a nano-adsorbent because it is effective against heavy metal ions (such as Pb). +2 Hg +2 Cd +2 And As +3 The binding affinity of TA-CPF to common threats can enable the extraction of heavy metals from produced water samples. The antimicrobial effects of TA-transition metal ion-coordinated CPF can be used in water disinfection and decontamination technologies. Incorporating TA-CPF into the most common commercial filtration membranes, polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF), to create highly porous, multifunctional CPF-based nanopads, filters, and membranes can be fabricated via electrospinning. These filters can be advantageously used in water purification processes from non-traditional water sources.

[0114] Materials fabricated using the methods disclosed herein can be used as fluorescence sensors at excitation wavelengths for contaminant detection and water quality monitoring. The materials disclosed herein can also form part of smart sensors that provide rapid and accurate detection of chemicals and pathogens. The combination of fluorescence signals received from polyphenolic units in tannins with long-range wavelength emission from transition metal ion centers can serve as a unique platform, allowing these materials to be used as sensing membranes for on-site analyte detection without the need for additional laboratory analysis.

[0115] The deployment of the coordination polymer framework in wastewater treatment and reuse depends on its high density of strong adsorption / binding sites, functional groups, and customizable pore size of the internal surface. The combination of tannic acid with silsesquioxane core structure and coordination with biocompatible transition metal ions (e.g., as shown in FIG. 8) can provide unique chemical, morphological, and physical properties that offer multiple capabilities for use as efficient, environmentally friendly, and low-cost molecular sieves for water treatment.

[0116] With the synthesis described herein, in one embodiment, three different metal ions (Fe +3 , Zn +2 , and Ni +2 ) coordinated TA-CPF nanostructures and multifunctional tannic acid-silsesquioxane nanoparticles (TA-NPs) can be developed. These three metals were chosen because of their respective intrinsic antimicrobial, optical, and magnetic behaviors and biocompatibility properties that make eco-friendly water treatment technologies a great potential. Controlling the experimental conditions and physical parameters of the self-assembly microstructure and nanoparticle formation, and the theoretical predictions of coordination complex formation through computational analysis, can lead to the development of robust and reproducible synthesis methods that can be widely used to fabricate biologic nanomaterials from other natural polyphenols and their derivatives.

[0117] The five pyrogallol and five catechol groups of the oxygen-rich tannic acid can provide coordination bonding sites for metal ions while offering a variety of interactions, including hydrogen bonding, π-π interactions, and hydrophobic interactions, to form the self-assembled hierarchical structure of the coordination polymer framework. Computational analysis reveals the most likely binding sites of the catechol and pyrogallol units of tannic acid with the selected metal ions and provides insights into their optical behavior and enhanced chemical, structural, and physical properties, including the binding energies of different metal ions. Density functional theory calculations can be used to assess the feasibility of metal ion binding to the active sites of tannic acid. Since the coordination complex framework is too large (a self-assembled unit of coordination complex), DFT (density functional theory) analysis can be applied to the monomeric coordination complex unit. The geometry-optimized structure of the coordination complex and the electronic potential distribution map can be obtained to understand the available functional binding sites in the complex for contaminant removal.

[0118] According to one embodiment, all electronic structure calculations were performed using the Gaussian 09 software package and their output files were analyzed using the GaussView 05 software. First, the molecular geometry optimization of tannic acid was performed using the B3LYP functional and the split valence 6-31G basis set. The same method can be used to re-optimize the geometry, but with multiple metal ions placed at multiple different positions around the catechol and pyrogallol units. The same method can be used, but this time using a hybrid basis set, applying the LANL2DZ pseudopotential (LANL stands for Los Alamos National Laboratory) to the metal ions and 6-31G to all other atoms. According to one embodiment, alternative calculations can be employed, including ethanol as an implicit solvent, but there will be no change in the ordering between positions or relative energy differences and the optimized positions of the metal ions, so they will not be included in further calculations. A more diffuse basis set (6-31+G) can also be applied to examine the effect of metal ion positions, taking into account the outer range of atomic radii. For different metal ion coordination complexes, the binding energies can be calculated and compared from the energies of the optimized geometries before and after complex formation.

[0119] According to one embodiment, Ni +2 and Zn +2 metal ion coordinated tannic acid CPFs were prepared utilizing the synthetic procedures developed in the previous work demonstrated in synthesis scheme 1 for the preparation of TA-Fe(III) CPF. The reaction parameters were optimized and the complex formation was monitored by collecting UV-visible spectral traces. According to one embodiment, these metal ion coordinated CPFs were fully characterized using FTIR, UV-visible spectroscopy, fluorescence spectroscopy, proton NMR, X-ray photoelectron spectroscopy (XPS), and powder XRD. According to one embodiment, the elemental mapping by STEM / EDS using TEM provided the transition metal ion coordination distribution. The morphology was observed using SEM and TEM. The thermal stability of the nanostructures was evaluated by thermogravimetric analysis. According to one embodiment, the porosity and surface area of the microstructures were analyzed from nitrogen adsorption isotherm at 77 K.

[0120] According to some embodiments, a sol-gel polymerization method was used to demonstrate the feasibility of fabricating TA-silsesquioxane nanoparticles from their silane precursors (see Figure 15Scheme 2) shown in the middle. A novel sol-gel reactive site functionalized TA-silane precursor was prepared by random functionalization of the catechol hydroxyl groups of tannic acid with p-(chloromethyl)-phenethyltrimethoxysilane. Base catalyzed hydrolysis and condensation of the TA-silane precursor produced spherical raspberry-like TA-silsesquioxane nanoparticles (TA-NPs) in fairly good yields. According to one embodiment, to prepare a series of differently sized particles with tailored porosity, a series of controlled experiments were conducted to adjust reaction parameters such as base concentration, solvent volume, and reaction time. The effect of base concentration on particle formation, particle size distribution, and particle morphology was investigated in ethanol solutions of fixed silane concentration. All necessary characterizations were performed to assess particle composition, crystallinity, thermal stability, surface area and pore distribution, and optical properties.

[0121] Due to the ability to incorporate a wide range of ligand compositions from reactive functional groups to fluorescent molecules, the range of materials that can be fabricated in this way is extremely diverse. Furthermore, this approach can provide the opportunity to introduce more organic properties into inorganic matrices. Increasing the organic content can produce retained 3-D structures in a homogeneous solution, rather than in typical surface functionalized nanoparticle aggregation observed in silica particles. The organic functional groups of these hybrid particles can achieve two functions: (1) modification of the inorganic core, and (2) improved compatibility with the host matrix. Chemical tailoring of the ligands using this approach can also extend the range of grafting / ligand chemistry to other applications, including natural polyphenol-based organic-inorganic hybrids.

[0122] Nanosorbents have significantly improved properties compared to traditional sorbents with extremely high specific surface area, short intra-particle diffusion distance, tunable pore size, and surface chemistry. The high specific surface area provides high sorption capacity. Furthermore, the high surface energy with high density of functionalities and size-dependent surface structure at the nanoscale can produce highly active sorption sites, leading to higher surface area normalized sorption capacity. The structure-property relationship, as well as in-depth analysis of the particle morphology and their pore distribution, can provide a foundation for studying their potential as nanosorbents for heavy metal and organic contaminant cleanup as well as water disinfection. The novel nanomaterials described herein have high nanoporosity and oxygen-rich binding sites with the performance of ideal nanosorbents for fast and efficient water treatment technologies. The tailored pore size, oxygen-rich high density multifunctionality, and coordinated transition metal ion nodes in TA-CPF can provide a new technological platform for selectively targeting various trace contaminants and microorganisms in wastewater.

[0123] According to one embodiment, TA-M +n -CPF and TA-NP nanobeads were tested for the removal of four selected heavy metal ions - Pb +2 , Hg +2 , Cd+2 and As +3 . According to one embodiment, the nanomaterials are tested for individual heavy metal ion extraction from solution, which can then be analyzed for the resulting heavy metal ion solution. Experimental studies are conducted to investigate the effects of contact time, initial pH, K + and Na + concentration, coexisting multivalent metal ions, and adsorption-desorption cycles on the adsorption process. In the pH dependency study, batch adsorption experiments are conducted and the heavy metal ion concentration after removal of the adsorbent is quantified by LC-MS spectroscopy. The adsorbent can also be analyzed by XPS and STEM / EDS to quantify the atomic percentage of adsorbed heavy metal ions. Adsorption-desorption cycle experiments can also be conducted simultaneously. According to one embodiment, adsorption and desorption mechanisms of heavy metal ions are investigated using adsorption kinetic plots and adsorption isotherms. Adsorption kinetics are determined at pre-determined concentrations and pre-determined pH values. The pseudo-first order and pseudo-second order kinetic models shown in equations (1) and (2) are applied to investigate the specific kinetic parameters of heavy metal ions adsorbed on TA-CPF.

[0124] ln(q e -q t ) = ln q e -k1t - (1)

[0125]

[0126] where q e (mg / g) is the equilibrium adsorption capacity; k1(min- 1 ) and k2(g / (mg min)) represent the rate constants for pseudo-first order and pseudo-second order adsorption, respectively. The values of k1and k2can be determined from the slope and intercept of the kinetic isotherm.

[0127] According to one embodiment, adsorption isotherms for each heavy metal ion on TA-CPF are measured by increasing the heavy metal ion concentration from 20 mg / L to 300 mg / L at 298 K and an optimized pH value, which is determined from initial studies. To investigate the adsorption behavior between heavy metal ions and TA-CPF, the equilibrium adsorption data are analyzed using the Langmuir and Freundlich models. The linear equations for the Langmuir and Freundlich models are shown in equations (3) and (4).

[0128]

[0129]

[0130] where q m (mg / g) and K Lrespectively, and a constant related to the free energy of adsorption. K F and n are constants of the Freundlich model.

[0131] According to one embodiment, when evaluating porous materials for water treatment applications, selectivity towards common organic or inorganic species, such as high concentrations of Ca 2+ , Mg 2+ , Na + , and K + , respectively, found in wastewater or surface water samples, is an important factor. While ions can compete for binding sites, organic species can complex metals in solution or block the pores of the adsorbent, thereby completely impairing capacity and / or removal rates. All four types of functional nanomaterials can be tested in selected water samples containing high concentrations of Hg 2+ and Pb 2+ .

[0132] According to one embodiment, the antimicrobial and antioxidant properties of tannic acid and three transition metal ions are exploited, in which the effectiveness of these novel nanomaterials for disinfecting water contaminated with bacteria is readily assessed. This assessment demonstrates that TA-CPF-based nanomaterials can be used to develop point-of-use disinfection devices to rapidly and effectively detect microorganisms in water. The ability of TA-M +n CPF materials to inactivate >99% of gram-negative and gram-positive bacteria, including E. coli, V. cholera, and (methicillin-resistant) S. aureus, in a short processing time can be tested. To this end, TA-M +n CPF and TA-NP nanobeads are coated on glass petri dishes, bacteria-contaminated water is added to the petri dishes, and incubated for a predetermined period of time. According to one embodiment, the amount of live bacteria remaining in the bulk water after treatment (denoted as "treated" water) is determined by standard colony forming unit (CFU) analysis and compared to the untreated sample (i.e., negative control). Notably, these bacteria (e.g., E. coli and V. cholera) are chosen based on their being some of the most common bacteria found in contaminated water supplies. In addition, methicillin-resistant S. aureus (MRSA) can also be investigated to determine the ability of the nanomaterials against antibiotic-resistant strains. Additional experiments are conducted to determine whether TA-CPF is feasible in large-scale operations.

[0133] The antimicrobial mechanism of TA-CPF coordinated with transition metal ions is as follows Figure 9It is believed that the bacteria are first adsorbed onto the nanomaterial surface and then inactivated by the biphenyldiol groups and transition metal ion nodes through a denaturation process, whereby the entire mechanism can proceed through a contact-activated mode. The data from the analysis of the antibacterial effect on the bulk water that can be treated in the well plate (CFU analysis) can only confirm the number of live bacteria that remain in the treated water sample, but cannot show the fate of those bacteria that have been adsorbed by the nanomaterial. It is believed that most of the bacteria adsorbed by the TA-CPF should be dead. To prove this, a series of various types of TA-CPF samples can be subjected to disinfection testing of E. coli contaminated water in a well plate system, and then the particles are crushed and the contents can be subjected to CFU analysis again to determine the viability of the bacteria adsorbed by the nanomaterial. This method of determining bacterial cell viability is comparable to the standard method for determining bacterial content in tissue samples for in vivo experiments. It is worth noting that the bulk water needs to be removed prior to crushing the particles.

[0134] The use of coordination polymer frameworks, specifically MOFs, as fillers in electrospun nanofibers has proven useful for gas separation systems. Electrospinning is a very low cost and simple technique for preparing membranes with relatively high flux, porosity, and mechanical strength compared to conventional methods of preparing mixed matrix membranes. The process requires very little material and little post-membrane processing, thus making it a more environmentally friendly technique. The organic portion of the MOF and the electrospun polymer are generally compatible, which makes uniform distribution of the MOF crystals at high loading rates, less aggregation possible. MOF-nanofiber membranes have been demonstrated in air pollution control, hydrogen storage, and other gas-related work. It is thereby demonstrated that it is advantageous to use electrospinning methods to manufacture nanoporous TA-CPs based nanomats, membranes, and filters on a large scale.

[0135] TA-CPF can be incorporated into the most common commercial filtration membranes, polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF) to make highly porous and multifunctional CPF-based nanomats, filters, and membranes. The mechanical properties, thermal and chemical stability can be evaluated for wastewater filtration and treatment to assess the suitability of these filters for water purification processes from non-traditional water sources.

[0136] In a typical manufacturing process, nanofibers are prepared by electrospinning after blending a TA-CPF derivative with polyacrylonitrile (PAN-15kDa, 10wt%). After preparing two solutions separately, a PAN / TA nanomaterial (1:1) solution is prepared: 10wt.% / vol% TA nanomaterial is added to the PAN solution (10wt.% / vol%), and the mixture is stirred for 12 hours to form a homogeneous solution. Approximately 10 mL of the prepared solution is then drawn into a 10 mL syringe for electrospinning. The syringe is placed in a syringe pump with a feed rate of 1 mL / h. The electrospinner is operated at 15 kV. The distance between the needle tip and the collector tip is set to 15 cm. Subsequently, the PAN / TA nanofibers are collected on aluminum foil attached to a stainless steel plate. After drying the nanofibers, they can be characterized using SEM (as shown in Figure 12) and FTIR to study the morphology and composition of the nanofiber composite. In this way, large-area nanofiber mats can be fabricated by combining TA-CPF.

[0137] Water quality monitoring is extremely challenging due to the extremely low concentrations of micropollutants, the high complexity of water and wastewater, and the lack of low-cost, rapid chemical and pathogen detection methods. Rapid multiplex detection of microorganisms and other pollutants is essential for diagnostic-based disinfection or biofilm control, as well as for heavy metal poisoning, where treatment decisions are made based on information from advanced sensors to provide efficient, responsive (flexible), and targeted remediation. Utilizing the photoluminescence quenching signal, a result of the binding of pollutants to the TA-CPF functional framework, could be advantageous for testing TA-CPF nanomaterials in multi-channel sensor devices capable of pollutant detection as well as water quality monitoring of chemicals and pathogens.

[0138] By selectively quenching the high photoluminescence intensity generated at a single excitation wavelength, TA-CPF can also act as a fluorescence quencher during the adhesion of microorganisms and chemical contaminants to the surface. Preliminary studies show that TA-NP and TA-Fe(III)CPF exhibit broad absorption and high fluorescence emission in the UV-visible region under excitation at 340 nm and 325 nm, respectively. Utilizing the optical properties of TA-CPF, fluorescent probes can be fabricated for multiple target detection. Figure 10 As shown, the design method can focus on fabricating nanoporous TA-CPF nanomaterial thin layers on PVDF and PAN filter pads or transparent flexible substrates. Placing a drop of contaminated water on the surface of the nanomaterial-coated substrate causes a decrease or increase in the luminescence intensity of the fluorescence signal due to contaminant binding to the nanomaterial surface. According to one embodiment, the prepared testing equipment, configured as shown, tests for a range of contaminants present in produced water and other non-traditional water samples. According to one embodiment, a calibration curve regarding the concentration of a specific contaminant versus the luminescence intensity is first formed before validating the sensor for real-time water quality monitoring.

[0139] According to one embodiment, in an exemplary device manufacturing process, a simple and cost-effective spray technique is used to coat a TA-CPF nanostructured water suspension on a transparent cross-linked polydimethylsiloxane (PDMS) substrate, enabling the production of large-area flexible modules. The influence of film thickness, particle concentration, and the number of cycles required for detection can be evaluated. According to one embodiment, after the coated film is exposed to visible light, while being excited at a selected wavelength, the fluorescence signal is measured.

[0140] Embodiments of the presently disclosed subject matter can introduce an innovative agro-ecological approach to water treatment from non-traditional water resources, enhancing the sustainability and resilience of agriculture and natural resources. It can provide: (1) the use of nanobiomaterials as composite nano-adsorbents from agricultural and forest-derived products - natural polyphenols; (2) the use of multiplexed smart fluorescent probes as point-of-use devices for rapid, accurate, and on-site water quality monitoring; and (3) the manufacture of molecular sieve adsorbents, filters, membranes, and pads with high surface area and high density functionality for selective metal ion extraction.

[0141] The embodiments of the invention listed above are accompanied by the following figures, schemes, pictures, chemical structures, and electron microscopy images. While the above methods have been explained with respect to lithium, the methods described herein can be implemented with other metals, and appropriate modifications can be made to accommodate the materials being treated.

[0142] Any dimensions listed above in the drawings and these descriptions are provided for exemplary purposes. Thus, not all embodiments within the scope of the drawings and these descriptions are made according to such exemplary dimensions. The drawings are not necessarily to scale. Thus, not all embodiments within the scope of the drawings and these descriptions are made according to the apparent proportions of the drawings. For each drawing, however, at least one embodiment is made according to the apparent relative proportions of the drawing.

[0143] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this presently disclosed subject matter belongs. Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the presently disclosed subject matter, representative methods, devices, and materials are now described.

[0144] Following long-standing patent law convention, the terms "a," "an," and "the" refer to "one or more" when used in the subject specification including claims. Thus, for example, reference to "a device" can include more than one such device, and so forth.

[0145] The description of various embodiments of the application is intended for purposes of illustration, and is not intended to exhaustively account for all possible embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application, or technical improvement over technologies found in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims

1. A method of synthesizing a tannic acid-coordinated Fe(III)-coordination polymer framework, TA-Fe(III)-CPF, the method comprising: coordinating tannic acid, TA, with acetic acid Fe(III) to produce a mixture of coordination complexes having different coordination stoichiometry between the pyrogallol units and the Fe(III) units; subjecting the mixture to ultrasonic vibrations for a predetermined time to initiate complex formation reactions; and forming a solid three-dimensional tannic acid-coordinated Fe(III)-coordination polymer framework, TA-Fe(III)-CPF, from the mixture, wherein Fe(III) ions bind to corresponding phenolic groups of tannic acid, TA, molecules after elimination of hydroxyl units of the tannic acid, TA, molecules, wherein the solid three-dimensional tannic acid-coordinated Fe(III)-coordination polymer framework comprises coordination bonds between Fe(III) and hydroxyl groups of pyrogallol moieties of tannic acid; wherein the solid three-dimensional tannic acid-coordinated Fe(III)-coordination polymer framework, TA-Fe(III)-CPF, comprises a plurality of nanoporous beads; wherein the nanoporous beads extract at least one alkali metal from an aqueous solution; the solid three-dimensional tannic acid-coordinated Fe(III)-coordination polymer framework, TA-Fe(III)-CPF, has pores with a cross-section of less than 2 nm.

2. The method of claim 1, further comprising: subjecting the solid three-dimensional tannic acid-coordinated Fe(III)-coordination polymer framework, TA-Fe(III)-CPF, to further ultrasonic vibrations; applying a centrifugal force to separate solid particles comprising TA-Fe(III)-CPF from the mixture; and, washing the solid particles with water to produce TA-Fe(III)-CPF nanoporous beads having nanoporosity.

3. The method of claim 1, wherein the ultrasonic vibrations are generated by an ultrasonic apparatus.

4. A method of synthesizing tannic acid-silsesquioxane nanoparticles, TA-NP, the method comprising: reacting tannic acid, TA, with silane precursors by Williamson ether synthesis to form sol-gel reaction sites on TA molecules to functionalize pyrogallol units within each tannic acid, TA, molecule backbone with silane precursors, wherein the silane precursors comprise organosilane precursors, wherein the sol-gel is formed by base catalyzed hydrolysis and condensation to convert monomers to polymers dispersed in a colloidal solution; forming integrated network sites on the periphery of the TA molecules to produce a crude product; subjecting the crude product to a vacuum to concentrate the crude product; washing the concentrated crude product with hexane to produce a refined product; treating the refined product with deionized water to remove unreacted TA to produce tannic acid-silsesquioxane nanoparticles, TA-NP, wherein the tannic acid-silsesquioxane nanoparticles, TA-NP, are spherical, wherein the tannic acid-silsesquioxane nanoparticles, TA-NP, comprise uniformly distributed nanopores; the tannic acid-silsesquioxane nanoparticles, TA-NP, have pores with a cross-section of less than 2 nm.

5. The method of claim 4, wherein the sol-gel reaction sites are formed by alkylating the hydroxyl groups of the phenolic units present in the tannic acid, TA, molecules with organosilane precursors.

6. The method of claim 4, wherein the organosilane precursors further comprise organoalkoxysilanes, wherein the benzyl units of the organoalkoxysilane molecules functionalize the pyrogallol hydroxyl groups of the tannic acid, TA, molecules.

7. The method of claim 4, further comprising: dispersing the sol-gel in a water-based solvent to produce a coating ink; and fabricating a nanoparticle soft dielectric film from the coating ink, the soft dielectric film comprising one or more of a flexible surface and an irregular surface.

8. The method of claim 4, further comprising: applying a centrifugal force to separate solid particles from the refined product; washing the solid particles with water; treating the solid particles with an ethanol solution; and, collecting the TA-NP particles in solid form.

9. The method of claim 4, wherein the carbonyl stretch of the silane molecules is lower than the ester carbonyl stretch of the tannic acid, TA, molecules.

10. The method of claim 4, wherein the TA-silane molecule portion of the tannic acid- silsesquioxane nanoparticle, TA-NP, is thermally stable up to 425 °C.

11. The method of claim 4, wherein the TA molecule portion of the tannic acid- silsesquioxane nanoparticle, TA-NP, is thermally stable up to 525 °C.

12. A method of extracting metal ions from an aqueous solution, the method comprising: providing a three-dimensional molecular sieve coordination polymer framework, CPF, material, wherein the three-dimensional molecular sieve coordination polymer framework, CPF, material is formed by coordinating tannic acid, TA, with Fe(III) acetate to produce a mixture of coordination complexes having different coordination stoichiometries between pyrogallol units and Fe(III) units, subjecting the mixture to ultrasonic vibrations for a predetermined period of time to initiate complex formation reactions, forming a coordination polymer framework from the mixture; wherein Fe(III) ions bind to corresponding phenolic groups of tannic acid, TA, molecules after elimination of hydroxyl units of the tannic acid, TA, molecules, wherein the three-dimensional molecular sieve coordination polymer framework, CPF, material comprises coordination bonds between Fe(III) and hydroxyl groups of pyrogallol moieties of tannic acid; wherein the three-dimensional molecular sieve coordination polymer framework, CPF, material comprises a plurality of nanoporous beads; the three-dimensional molecular sieve coordination polymer framework, CPF, material has pores with a cross-section less than 2 nm; and passing a liquid substance through the molecular sieve, CPF, material to extract metal ions present in the liquid substance.

13. The method of claim 12, wherein the metal ions comprise one or more of alkali metals, transition metals, and heavy metals.

14. The method of claim 12, wherein the metal ions comprise lithium, wherein the lithium is recovered as one or more of lithium carbonate and lithium ion-coordinated CPF.

15. The method of claim 12, wherein the liquid substance comprises one or more of saltwater and non-traditional water sources.

16. The method of claim 12, wherein the molecular sieve coordination polymer framework (CPF) material comprises pores, wherein the cross-section of the pores is tailored to the size of the metal ion to be extracted.

17. The method of claim 12, wherein the molecular sieve coordination polymer framework (CPF) material exhibits a red-shift peak at 330 nm when observed under ultraviolet-visible spectrophotometer.

18. The method of claim 12, wherein the molecular sieve coordination polymer framework (CPF) material is in one or more forms of microparticles, nanoparticles, nanorods, nanobelts, and nanobeads.

19. The method of claim 12, wherein the molecular sieve coordination polymer framework (CPF) material is in one or more forms of filters, gaskets, membranes, adsorbent beads, packing materials, point-of-use fluorescent probes, and filter pads.

20. The method of claim 12, further comprising one or more of using the molecular sieve coordination polymer framework (CPF) material for multiplex detection of heavy metal ions or pollutants, selective extraction of the heavy metal ions or pollutants, disinfection of water, and purification of water.

21. A method of extracting lithium from lithium-containing brine, the method comprising: passing the lithium-containing brine through a filter comprising a nanoporous molecular sieve coordination polymer framework (CPF) material to extract lithium ions present in the lithium-containing brine, wherein the nanoporous molecular sieve coordination polymer framework (CPF) material is formed by coordinating tannic acid (TA) with Fe(III) acetate to produce a mixture of coordination complexes having different coordination stoichiometry between pyrogallol units and Fe(III) units, subjecting the mixture to ultrasonic vibrations for a predetermined period of time to initiate complex formation reactions, forming the nanoporous molecular sieve coordination polymer framework material from the mixture; wherein Fe(III) ions bind to corresponding phenolic groups of tannic acid (TA) molecules after elimination of hydroxyl units of the tannic acid (TA) molecules, wherein the nanoporous molecular sieve coordination polymer framework (CPF) material comprises coordination bonds between Fe(III) and hydroxyl groups of pyrogallol moieties of tannic acid (TA); wherein the nanoporous molecular sieve coordination polymer framework (CPF) material comprises a plurality of nanoporous beads; the nanoporous molecular sieve coordination polymer framework (CPF) material has pores with a cross-section less than 2 nm; reacting the lithium ions with the nanoporous molecular sieve coordination polymer framework (CPF) material to form a lithium ion-coordinated CPF nanocomposite; and capturing a filtrate residue after removing the lithium ion-coordinated CPF nanocomposite.

22. The method of claim 21, further comprising treating the lithium ion-coordinated CPF nanocomposite with carbonic acid to produce lithium carbonate.

23. The method of claim 21, further comprising compacting and bagging the lithium ion-coordinated CPF nanocomposite.

24. The method of claim 21, further comprising passing the filtrate residue through a nanoporous coordination polymer framework (CPF) filtration material to extract or remove one or more of a contaminant and a heavy metal ion present in the filtrate residue.

25. The method of claim 24, further comprising boiling and condensing the filtrate residue to produce usable water.

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