Systems, devices, and methods for separation of metals from waste, scrap, and post-consumer products

Abstract

The present disclosure includes systems, devices, and methods for separating metals from metal-containing compositions including compositions derived from (e.g., leached from) waste, scrap, and post-consumer products. Various compositions include a plurality of porous metal-organic framework / polymer composite particles (MOF / polymer composite particles), the plurality of MOF / polymer composite particles including a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF. The plurality of MOF / polymer composite particles capture a metal from a metal-containing composition.

Description

SYSTEMS, DEVICES, AND METHODS FOR SEPARATION OF METALS FROM WASTE, SCRAP, AND POST-CONSUMER PRODUCTSRELATED APPLICATION

[0001] This patent application is a NON-PROVISIONAL patent application claiming priority to U.S. Provisional Patent Application No. 63 / 712,423, filed on 26 October 2024 and entitled “SYSTEMS, DEVICES, AND METHODS FOR SEPARATION OF METALS FROM SOLID INPUTS,” which is incorporated in its entirety herein.FIELD OF THE DISCLOSURE

[0002] The present disclosure relates to extracting metal from a metal-containing composition and, more particularly, the present disclosure relates to extracting metal from a metal-containing composition using metal-organic frameworks (MOF) and / or MOF / polymer composite particles.BACKGROUND OF THE DISCLOSURE

[0003] Metals are used throughout the world economy in industries related to the manufacture and use of products ranging from consumer electronics, batteries, electric vehicles, wind turbines, solar cells, and emerging new technologies. Some such metals (e.g., mercury, lead, and the like) may be environmentally damaging and detrimental to health. Other such metals may have economic value, particularly those that are in low natural abundance. Accordingly, extraction of these metals from metal-containing compositions (e.g., industry waste stream compositions) can have significant economic, environmental, and strategic implications.

[0004] Traditional methods for extracting metals, particularly valuable metals (e.g., gold, copper, and the like), from metal-containing compositions typically include chemical precipitation generally employing the use of strong acids or cyanides to dissolve and separate the metals from the waste-containing compositions. Other methods include ion exchange, chemical coagulation, and electrochemical technologies. However, such methods often suffer from various disadvantages including the need for an abundance of chemicals, many of which are highly toxic, high-energy consumption (e.g., high temperature), high cost, and low reaction efficiencySUMMARY OF THE DISCLOSURE

[0005] Systems and / or devices disclosed herein may be configured as, for example, a reactor and / or a continuous flow device comprise a chamber and / or container with a cavity, an inlet port, and an outlet port. The cavity may be configured to hold a volume of, for example, a metal-containing composition (an oxidizing agent, an organic halide, an inorganic halide, a chelating agent, a binding agent, an acid, a base, and any combination thereof) and / or hold a volume of material (e.g., a leachate, water, etc.) into which metal is, or will be, dissolved, and / or a plurality of porous metal-organic framework / polymer composite (MOF / polymer composite) particles. Exemplary metal-containing compositions include, but are not limited to water, tap water, wastewater, sea water, wastewater from electronic waste, electronic waste, solar cell waste, evaporator scrap waste, mining waste, refining waste, minerals, ores, mine tailings, slag, ash, fly ash, dust, trash, photographic film waste, medical film waste, jewelry waste, dental waste, sewage sludge, industrial byproduct waste, and any combination thereof. Additionally, or alternatively, the metalcontaining composition is selected from the group consisting of N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, nicotinic acid, 1,3-Dibromo-5,5-Dimethylhydantoin, pyridine, pyrazine, niacin, derivatives thereof, and any combination thereof. The chamber may may comprise, for example, a polymer, a plastic, a metal, a metal alloy, and any combination thereof. Inlet port may be configured to allow material (e.g., a metal-containing composition, water, leachate, etc.) to enter the cavity and outlet port may be configured to allow material to exit the cavity.

[0006] The systems and / or devices disclosed herein may further include a plurality of MOF / polymer composite particles (e.g., a volume of 5 grams to 100,000 kilograms) that comprise a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, the active-redox monomers polymerized to form a plurality of active-redox polymers, wherein the plurality of MOF / polymer composite particles are configured to capture or react to a metal (e.g., a transition metal, a rare earth metal, a platinum group metal, or a precious metal) of a metal-containing composition disposed within the chamber. In some embodiments, the active-redox monomers are bound to at least the portion of the plurality of unsaturated open metal coordination sites of theMOF. At times, the MOF may be an iron-based MOF and / or the composition of the MOF may include iron ions. Additionally, or alternatively, the MOF may be a MIL-series MOF, and / or a PCN-series MOF.

[0007] The active-redox monomers may include, for example, phenylenediamine-based monomers, triarylamine-based monomers, hemin-based monomers, ferrocene-containing monomers, polypyridyl monomers, quinone-based monomers, catechol-functionalized monomers, pyrogallol-based monomers, viologen-based monomers, isomers thereof, co-monomers thereof, and any combination thereof. Additionally, or alternatively, the active-monomers may include, but are not limited to, p-phenylenediamine; o-phenylenediamine; m-phenylenediamine; 2-methyl-m-phenylenediamine; 4-methyl-m-phenylenediamine; trimethyl-m-phenylenediamine; N, N'-bis(4-aminophenyl)-N, N'-di(4-methylphenyl)-1,4-phenylenediamine; N, N'-bis(4-methoxyphenyl)-N, N'-bis(4-(4-aminophenyl-4'-methoxyphenylamino)phenyl)-p-phenylenediamine; 4-(bis(4-methylphenyl)amino)benzoic acid; 4-(bis(4-methoxyphenyl)amino)benzoic acid; 1,1'-bis(hydroxymethyl)ferrocene; ferrocenecarboxaldehyde; 2-ferrocene-ethyl-2-oxazoline; 1,1'-bis(phenylphosphine)ferrocene; 2,2'-Bipyridine; ruthenium tris(2,2'-bipyridine);2,2':6',2"-terpyridine; 1,10-phenanthroline; quaterpyridine; pyridine-bis(oxazoline); pyridine-oxazoline; p-hydroquinone; disodium 4,5-dihydroxy-1,3-benzenedisulfonate; 2,5-bis((dimethylamino)methyl)benzene-1,4-diol; 2-Methoxy-1,4-hydroquinone; dopamine methacrylamide; 4-vinyl catechol; 3-vinyl catechol; chlorodopamine methacrylamide; N-(prop-2-yn-1-yl)dopamine; 3,4-dihydroxyphenylalanine; N'-(4-vinylbenzyl)-methylviologen; N, N'-dimethyl-4,4'-bipyridinium dicholoride; isomers thereof; co-monomers thereof; and any combination thereof.

[0008] The MOF / polymer composite particles have a size of, for example, 0.1 micrometers to 10,000 micrometers and, on some occasions, may be treated with a binder like a polymer(s) and / or inorganic metal(s). When the MOF / polymer composite particles are treated with a polymer binder, the polymer binder may be, for example, polyvinyl alcohol, polyvinyl butyral, polyethersulfone, and poly(methyl methacrylate), polyethersulfone, polyvinyl pyrrolidone, polyetherimide, polystyrene, cellulose acetate, polytetrafluoroethylene, polyvinyl formal, starch, and / or any combination thereof. When the MOF / polymer composite particles are treated with an inorganic metal binder, the inorganic metal binder may be, for example, graphite, alumina, silica, and any combination thereof.

[0009] The compositions disclosed herein may comprise a plurality of porous metal-organic framework / polymer composite (MOF / polymer composite) particles comprising a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites and one or more active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, wherein the plurality of MOF / polymer composite particles are configured to capture or react to a metal of a metal-containing composition.

[0010] The active-redox monomers may be bound to at least the portion of the plurality of unsaturated open metal coordination sites of the MOF by coordinate covalent bonds. Exemplary active-redox monomers may be, for example, phenylenediamine-based monomers, triarylamine-based monomers, hemin-based monomers, ferrocene-containing monomers, polypyridyl monomers, quinone-based monomers, catechol-functionalized monomers, pyrogallol-based monomers, viologen-based monomers, isomers thereof, co-monomers thereof, and any combination thereof. On some occasions, the MOF may be an iron-based MOF and / or a composition of the MOF may include iron ions, an MIL-series MOF, and / or a PCN-series MOF.

[0011] The active-monomers of the composition may be, for example, p-phenylenediamine; poly(o-phenylenediamine); o-phenylenediamine; m-phenylenediamine; 2-methyl-m-phenylenediamine; 4-methyl-m-phenylenediamine; trimethyl-m-phenylenediamine; N, N'-bis(4-aminophenyl)-N, N'-di(4-methylphenyl)-1,4-phenylenediamine; N, N'-bis(4-methoxyphenyl)-N, N'-bis(4-(4-aminophenyl-4'-methoxyphenylamino)phenyl)-p-phenylenediamine; 4-(bis(4-methylphenyl)amino)benzoic acid; 4-(bis(4-methoxyphenyl)amino)benzoic acid; 1,1'-bis(hydroxymethyl)ferrocene; ferrocenecarboxaldehyde; 2-ferrocene-ethyl-2-oxazoline; 1,1'-bis(phenylphosphine)ferrocene; 2,2'-Bipyridine; ruthenium tris(2, 2'-bipyridine); 2,2':6',2"-terpyridine; 1,10-phenanthroline; quaterpyridine; pyridine-bis(oxazoline); pyridine-oxazoline; p-hydroquinone; disodium 4, 5-dihydroxy-1, 3-benzenedisulfonate; 2,5-bis((dimethylamino)methyl)benzene-1,4-diol; 2-Methoxy-1,4-hydroquinone; dopamine methacrylamide; 4-vinyl catechol; 3-vinyl catechol; chlorodopamine methacrylamide; N-(prop-2-yn-1-yl)dopamine; 3,4-dihydroxyphenylalanine; N'-(4-vinylbenzyl)-methylviologen; N, N'-dimethyl-4,4'-bipyridinium dicholoride; isomers thereof; co-monomers thereof; and any combination thereof.

[0012] The MOF / polymer composite particles have a size of 0.1 micrometers to 10,000 micrometers and, on some occasions, may be treated with a binder such as a polymer (e.g., polyvinyl alcohol, polyvinyl butyral, polyethersulfone, and poly(methyl methacrylate), polyethersulfone, polyvinyl pyrrolidone, polyetherimide, polystyrene, and / or cellulose acetate), polytetrafluoroethylene, polyvinyl formal, starch, and / or an inorganic metal (e.g., graphite, alumina, silica, and any combination thereof).

[0013] The metal-containing composition may be, for example, tap water, wastewater, sea water, wastewater from electronic waste, electronic waste, solar cell waste, evaporator scrap waste, mining waste, refining waste, minerals, ores, mine tailings, slag, ash, fly ash, dust, trash, photographic film waste, medical film waste, jewelry waste, dental waste, sewage sludge, industrial by-product waste, and any combination thereof.

[0014] Exemplary methods disclosed herein comprise exposing a metal-containing composition to a plurality of porous metal-organic framework / polymer composite particles (MOF / polymer composite particles) like the MOF / polymer composite particles disclosed herein. In some cases, the exposure may be adding the metalcontaining composition to a container of a continuous flow (e.g., a continuous flow rate of 100 milliliters per minute to 2000 milliliters per minute) and / or reactor device housing the MOF / polymer composite particles and / or flowing the metal-containing composition through a container of a continuous flow and / or reactor device housing the MOF / polymer composite particles. In some cases, the method may further include stirring, or agitating, the metal-containing composition to a plurality of porous metal-organic framework / polymer composite particles (MOF / polymer composite particles) to, for example, increase a concentration of metal leaching into the metalcontaining composition and / or increases capture of a metal by the MOF / polymer composite particles. The method of claim 31, wherein flowing the metal-containing composition through the internal chamber at a continuous flow rate.

[0015] In some embodiments, the systems, devices, and / or methods disclosed herein may be configured to operate (e.g., the reacting and / or flowing of metalcontaining composition and / or the metal capturing) may be performed at a pH between approximately 0 and 12, a pH between approximately 2 and 10, a pH between approximately 4 and 8, a pH between approximately 5 and 9, a pH between approximately 6 and 8, and a pH of approximately 7.

[0016] In some embodiments, the devices and / or systems disclosed herein may be a filtration device that includes a filter housing, an internal mesh chamber, and a plurality of porous metal-organic framework / polymer composite (MOF / polymer composite) particles like the MOF / polymer composite particles disclosed herein may be disposed within the internal mesh chamber. The plurality of MOF / polymer composite particles may comprise a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, the active-redox monomers polymerized to form a plurality of active-redox polymers, wherein the plurality of MOF / polymer composite particles are configured to capture a metal from a metal-containing composition within the internal mesh chamber.

[0017] The filter housing may comprise a polymer, a plastic, a metal, and / or a metal alloy and the internal mesh chamber may be, for example, a stainless steel mesh and / or a mesh made from a polymer or plastic. In some embodiments, the internal mesh chamber may be cylindrical in shape with a height of 2 inches to 12 inches, a diameter of 0.5 inches to 7 inches and / or has a length to diameter ratio of 2 to 4. The internal mesh chamber may be configured to house the plurality of MOF / polymer composite particles disposed therein in a volume of 5 grams to 100,000 kilograms.

[0018] According to some embodiments, the present disclosure provides a filter device. The filter device includes a filter housing and an internal chamber. Within the internal chamber, a plurality of metal-organic framework / polymer composite particles (MOF / polymer composite particles) are disposed. The MOF / polymer composite particles include a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF. The active-redox monomers polymerized to form a plurality of active-redox polymers. The plurality of MOF / polymer composite particles capture a metal from a metal-containing composition within the internal chamber.

[0019] In other aspects, the present disclosure provides a composition including a plurality of metal-organic framework / polymer composite particles (MOF / polymer composite particles). The MOF / polymer composite particles include a porous metalorganic framework (MOF) with a plurality of unsaturated open metal coordinationsites and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF. The active-redox monomers polymerized to form a plurality of active-redox polymers. The plurality of MOF / polymer composite particles capture a metal from a metal-containing composition.

[0020] In yet other embodiments, the present disclosure provides a method of capturing a metal in a metal-containing composition. The method includes providing a filter device having a filter housing with an inlet port and an outlet port, and an internal chamber. Alternatively, the method includes providing a continuous flow device or reactor having an internal chamber with an inlet port and an outlet port. Within the internal chamber, a plurality of metal-organic framework / polymer composite particles (MOF / polymer composite particles) are disposed. The MOF / polymer composite particles include a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF. The active-redox monomers polymerized to form a plurality of active-redox polymers. The method further includes flowing the metalcontaining composition through the internal chamber into the inlet port and out of the outlet port and capturing, with the plurality of MOF / polymer composite particles, a metal from the metal-containing composition within the internal chamber.

[0021] Any combinations of the various embodiments and implementations disclosed herein can be used in a further embodiment, in any combination, consistent with the disclosure. These and other aspects and features can be appreciated from the following description of certain embodiments presented herein in accordance with the disclosure and the accompanying drawings and claims.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The present disclosure is illustrated by way of example, and not limitation, in the figures of the accompanying drawings in which:

[0023] FIG. 1 is a schematic representation of an exemplary process for polymerization inside of MOFs, wherein a MOF / polymer composite, in accordance with some embodiments of the present disclosure;

[0024] FIGS. 2A-2F provide a series of photographs of MOF / polymer composite particles and granules of various sizes, in accordance with some embodiments of the present disclosure;

[0025] FIG. 3 provides a flowchart illustrating an exemplary process for extracting metal from a metal-containing composition in accordance with some embodiments of the present disclosure;

[0026] FIG. 4 provides a flowchart illustrating an exemplary process for performing the process of FIG. 3 to specifically extract copper and gold from a solid matrix, in accordance with some embodiments of the present disclosure;

[0027] FIG. 5A provides a block diagram of an exemplary process for extracting metals from a solid matrix, in accordance with some embodiments of the present disclosure;

[0028] FIG. 5B provides a diagram showing an exemplary manner in which metals may be digested and / or extracted from a solid matrix, in accordance with some embodiments of the present disclosure;

[0029] FIG. 6A is a graph depicting results from an X-ray diffraction (XRD) of goldladen MOF / polymer composite, in accordance with some embodiments of the present disclosure;

[0030] FIG. 6B is a graph depicting results from an X-ray photoelectron spectroscopy (XPS) of gold-laden MOF / polymer composite, in accordance with some embodiments of the present disclosure;

[0031] FIG. 7A provides a photograph of a volume of copper-infused effluent from the MOF / polymer composite, in accordance with some embodiments of the present disclosure;

[0032] FIG. 7B provides a photograph of a volume of copper-depleted effluent from which copper has been extracted after electrochemical purification, in accordance with some embodiments of the present disclosure;

[0033] FIGS. 7C and 7D are graphs showing PXRD analysis results of the purified copper from electrodeposition compared to a simulated diffractogram of purified copper, in accordance with some embodiments of the present disclosure;

[0034] FIG. 7E provides a graph plotting copper concentration in parts per million (ppm) of copper-infused effluent over time during the electrowinning process, in accordance with some embodiments of the present disclosure; and

[0035] FIG. 8 provides a schematic diagram of a system configured to, for example, perform process(es) of FIGS. 3 and / or 4, in accordance with some embodiments of the present disclosure.

[0036] Throughout the drawings, the same reference numerals, and characters, unless otherwise stated, are used to denote like features, elements, components, or portions of the illustrated embodiments. Moreover, while the subject disclosure will now be described in detail with reference to the drawings, the description is done in connection with the illustrative embodiments. It is intended that changes and modifications can be made to the described embodiments without departing from the true scope and spirit of the subject disclosure as defined by the appended claims.DETAILED DESCRIPTION OF THE DISCLOSURE

[0037] The following sections describe certain embodiments of this disclosure, referencing the accompanying figures. Consistent reference numbers identify similar elements across different figures. This detailed description includes specific technical details to provide a more thorough understanding of the subject matter. However, those skilled in the art will recognize that the disclosed embodiments can be implemented and practiced without all the specific details provided. Some well-known features are not described in detail to keep the description focused and accessible. Additionally, the scale of elements shown in the figures may be adjusted without affecting the scope of this disclosure.

[0038] Embodiments described herein include systems, devices, compositions, and methods that relate generally to extracting (e.g., sequestering or separating) metal from a metal-containing composition (e.g., metal-containing waste composition) and, more particularly, the present disclosure relates to extracting metal from a metalcontaining composition using metal-organic frameworks (MOFs) and / or MOF / polymer composite particles (composition(s) of matter). The present disclosure includes systems, devices, compositions, and methods for extracting and / or purifying metals from fluid and / or solid inputs, such as metal-containing waste compositions, and / or purifying them in many cases. As used herein, the term "fluid" refers to liquid phase fluids and gas phase fluids and may be entrained with solid materials (e.g., sludge, precipitates, particulates, etc.). The fluid and solid inputs of the present disclosure may comprise waste compositions (e.g., from an industrial waste source such as electronic waste or mining waste or evaporator scrap waste).

[0039] Advantageously, the present disclosure overcomes various limitations of traditional methods of metal extraction from metal-containing compositions by achieving improved and / or high metal separation reaction efficiency while reducing or eliminating the use of toxic chemicals, reducing costs, reducing waste products, and reducing energy consumption (e.g., reduced processing temperatures).Specifically, the present disclosure comprises systems, devices, compositions, and methods that utilize one or more filters that include one or more types of MOFs and / or MOF / polymer composite particles to achieve these advantages. For example, metal separation from metal-containing compositions of the present disclosure advantageously avoids the use of toxic or highly toxic chemicals, such as strong acids or cyanides, carcinogens, pollutants, or acutely toxic chemicals.Moreover, the metal separation techniques described herein may be performed at pH values at or near neutral (~pH 7.0), at temperatures at or near room temperature (~20°C - 25°C), and at pressures at or near ambient pressure (~1 atmosphere).

[0040] As described above, the systems, devices, compositions, and methods disclosed herein utilize one or more filters that include one or more types of MOFs and / or MOF / polymer composite particles to extract metals from metal-containing compositions. As used herein, the term "metal-containing composition," and grammatical variants thereof, refers to a fluid, solid, solution, leachate, and / or complex fluid (e.g., water) mixture derived from a waste source, such as an industrial waste stream derived from the manufacture or processing of an industrial product (e.g., a semiconductor chip, electronic device, and / or metal ore).

[0041] Various metal-containing compositions in any form from waste sources that may be applicable to the present disclosure include, but are not limited to, tap water, wastewater, sea water, wastewater from electronic waste, electronic waste (e.g., circuit boards, computer parts, smartphones, other appliances, and the like), solar cell waste, solid and / or fluid (e.g., effluent) mining waste, solid and / or fluid (e.g., effluent) refining waste, different minerals, ores, mine tailings, slag, ash, fly ash, dust, trash, photographic film waste, medical (e.g., x-ray) film waste, jewelry waste, dental waste (e.g., dental alloy waste), sewage sludge, other industrial by-products, evaporator scrap waste, and any combination thereof. Waste sources may comprise valuable metals, as well, such as gold, copper, cobalt, tellurium, platinum, gallium, and various rare earth metals, among others including those described herein.

[0042] The various filters of the present disclosure comprise one or more types of MOFs and / or MOF / polymer composite particles. The MOFs disclosed herein may be selected and / or manufactured to have high porosity, high surface area, and / or high / diverse functionality (e.g., ability to adsorb large quantities of one or more guest species, such as metals). In some embodiments, a composition and / or architecture of a MOF and / or MOF / polymer composite may be tailored and / or tuned to capture specific metals (e.g., gold or copper), groups of metals (e.g., aluminum, lead, nickel, tin, zinc, iron, silver, platinum group metals, transition metals, precious metals, and / or rare earth metals), energy relevant metals, and / or other materials.

[0043] For exemplary purposes, the systems, devices, compositions, and methods of the present disclosure will be described with reference to the efficient recovery of copper and gold from metal-containing compositions derived from electronic waste. However, those of skill in the art will appreciate that the systems, devices, compositions, and methods disclosed herein may be used to recover metals other than copper or gold and / or compounds from any one or more variety of solid and / or fluid metal-containing compositions derived from waste, including those described herein.

[0044] In some embodiments, the MOFs described herein may be synthesized using iron sulfate (which is less toxic than iron chloride) at, for example, room temperature in ambient pressure conditions. The synthesized MOF may exhibit high porosity and crystallinity characteristics. Subsequent polymerization of the synthesized MOF (thereby creating a MOF / polymer composite) adds features that enable selectivity of the metal(s) or compounds to be extracted (e.g., sequestered) from a metal-containing composition derived from a waste source. In some embodiments, other iron-based MOF structures and / or MOF compositions that include iron ions may be used in accordance with the embodiments of the present disclosure, such as MIL-series MOFs (e.g., MIL-53, MIL-88 (A / B), MIL-100, MIL-101), PCN-series MOFs (e.g., PCN-250), and the like, and any combination thereof.

[0045] In some embodiments, the MOF / polymer composite may be prepared by first synthesizing a microcrystalline MOF structure (e.g., iron sulfate MOF), which may act as the rigid porous template for the MOF / polymer composite. In some instances, the MOF structure may comprise iron (Fe) trimer clusters that are linked together by, for example, benzenetricarboxylate ligands, resulting in a zeolite MTN topology, where the structure consists of apertures that are 0.5 nm and 0.8 nm indiameter into 2.5 nm and 2.9 nm sized cages. This architecture may allow metal ions to diffuse into the MOF structure, while preventing large complex organic compounds from entering, which may enhance its ability to isolate metal ions from simple and / or complex (e.g., with diverse waste contaminants) metal-containing compositions.

[0046] The MOF structure of the present disclosure comprises a plurality of unsaturated open metal coordination sites along the MOF's pore surface. As used herein, the terms "unsaturated open metal site" or "unsaturated open metal coordination site," and grammatical variants thereof, refers to a Lewis acidic metal center within the MOF structure that is not coordinated or fully coordinated or bound with guest species, such as metals. By taking advantage of the unsaturated open metal sites along the MOF’s pore surface, p-phenylenediamine (PpPDA) (a redoxactive monomer) is introduced into the MOFs porous network, binds to one or more of the unsaturated open metal sites, and undergoes an in-situ polymerization process thus creating the MOF / polymer composite shown in FIG. 1 and discussed herein.

[0047] The MOF / polymer composite may act as a porous template and / or may introduce extrinsic porosity to intrinsically non-porous polymers giving rise to high surface area accessible adsorption sites pinned along the MOF’s interior nanopore surface. In many cases, the MOF / polymer composite material retains its porous nature, mechanical properties of the MOF, and / or chemical functionality of the polymer all in one material system.

[0048] In one or more aspects, the PpPDA (or other redox-active monomer) binds to the unsaturated open metal sites of the MOF pore structure via a coordinate covalent bond (e.g., a dative bond). For example, the Lewis acidic metal center (e.g., atom or ion) of the MOF structure accepts a pair of electrons from the PpPDA (or other active-redox monomer) as a Lewis base ligand donor. Thereafter, polymerization of the PpPDA (or other active-redox monomer) occurs to form the polymer in the MOF / polymer composite. Polymerization may proceed, for example, by redox polymerization.

[0049] An active polymer (e.g., an active-redox polymer) is the fundamental contributor to the enhanced metal extraction capabilities of the MOF / polymer composite particles of the present disclosure. In some cases, the active polymer may be comprised of a plurality of redox-active monomers. In one or more aspectsof the present disclosure, the redox-active monomers may include, for example, phenylenediamine-based monomers and isomers thereof (e.g., ortho-phenylenediamine, mefa-phenylenediamine, and / or methyl-substituted phenylenediamines), triarylamine-based monomers, hemin-based monomers (e.g., hemin-acrylate monomers), ferrocene-containing monomers (e.g., vinylferrocenes, ferrocenylmethyl methacrylates, ferrocene / disulfide-containing methacrylates, ferrocene-tyrosine methacrylates), polypyridyl monomers, quinone-based monomers (e.g., p-benzoquinones, benzoquinone disulfonic acids, (Dimethylamino)methyl-hydroquinones)), catechol-functionalized monomers (e.g., halogenated dopamine methacrylamides, alkynyl catecholamines), pyrogallol-based monomers, viologen-based monomers, co-monomers thereof, and the like, and any combination thereof.

[0050] Specific examples of suitable active-redox monomers for use in forming the MOF / polymer composite particles of the present disclosure may include, but are not limited to, PpPDA; poly(o-phenylenediamine); o-phenylenediamine; m-phenylenediamine; 2-methyl-m-phenylenediamine; 4-methyl-m-phenylenediamine; trimethyl-m-phenylenediamine; N, N'-bis(4-aminophenyl)-N, N'-di(4-methylphenyl)-1,4-phenylenediamine; N, N'-bis(4-methoxyphenyl)-N, N'-bis(4-(4-aminophenyl-4'-methoxyphenylamino)phenyl)-p-phenylenediamine; 4-(bis(4-methylphenyl)amino)benzoic acid; 4-(bis(4-methoxyphenyl)amino)benzoic acid; 1,1'-bis(hydroxymethyl)ferrocene; ferrocenecarboxaldehyde; 2-ferrocene-ethyl-2-oxazoline; 1,1'-bis(phenylphosphine)ferrocene; 2,2'-Bipyridine; ruthenium tris(2, 2'-bipyridine); 2,2':6',2"-terpyridine; 1,10-phenanthroline; quaterpyridine; pyridine-bis(oxazoline); pyridine-oxazoline; p-hydroquinone; disodium 4,5-dihydroxy-1,3-benzenedisulfonate; 2,5-bis((dimethylamino)methyl)benzene-1,4-diol; 2-Methoxy-1,4-hydroquinone; dopamine methacrylamide; 4-vinyl catechol; 3-vinyl catechol; chlorodopamine methacrylamide; N-(prop-2-yn-1-yl)dopamine; 3,4-dihydroxyphenylalanine; N'-(4-vinylbenzyl)-methylviologen; N, N'-dimethyl-4,4'-bipyridinium dicholoride; co-monomers thereof; and the like; and any combination thereof.

[0051] Turning now to the figures, FIG. 1 is a schematic representation of an exemplary process for polymerization inside of MOFs, wherein a MOF / polymer composite 100 including a plurality of MOFs 110 with unsaturated open metal sites (shown as small squares 110a) configured to activate polymerization and placing the resulting MOF / polymer composite 100 into a filter 150. MOF / polymer composite 100comprises a MOFs array 110 with a plurality of MOF pores 120 with catalytically active sites 115 and, when a monomer 125, such as redox-active monomers, enter MOF pores 120, a MOF pore with monomers present therein 130 is created. Once in a MOF pore 120, monomers 125 begin to bond (e.g., covalently bond) to the actively catalytic sites 115, thereby forming a polymer coat on the inside of the MOF pore, thereby creating a polymerized MOF pore 140 of the MOF / polymer composite as shown in FIG. 1. In some cases, polymerized MOF pores 140 may be referred to herein as “MOF / polymer composite” and / or “granules of MOF / polymer composite”

[0052] Once created, polymerized MOF pores 140 may be placed within a filter housing 152 that has an internal chamber 155 in which to house polymerized MOF pores 140, an inlet port 160 for receiving a metal-containing composition, and an outlet port 165 for discharging the metal-containing composition after the polymerized MOF pores 140 capture metals therein (i.e., a portion of the metalcontaining composition). The filter housing 152 may be composed of, for example, a polymer and / or plastic (e.g., polypropylene, polystyrene, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate), a metal (e.g., stainless steel), metal alloys, and the like, and any combination thereof.

[0053] In some embodiments, filter 150 may include a stainless steel mesh column into which granules of MOF / polymer composite (i.e., polymerized MOF pores 140) are placed in a packed bed column and a metal-containing composition may be introduced to filter 150 via inlet port 160 so that it flows though the packed bed column of MOF / polymer composite with the assistance of, for example, gravity and / or a pump. In some cases, the backed bed column of the MOF / polymer composite may be configured to prevent channeling. In some embodiments, a structure and / or configuration of filter 150 may be configured to prevent excessive pressure drop across the packed bed column therein and / or ensure stability over time and operation in a packed bed column.

[0054] In some embodiments, the MOF / polymer composite 140 may be processed via, for example, a gravity tumble mechanism and / or a disc granulator to, for example, convert smaller particles of MOF / polymer composite 140 to larger-sized granules of MOF / polymer composite 140 of, for example, 250 pm - 500 pm in size (e.g., diameter) (or 250 pm to 375 pm, or 375 pm to 500 pm, or 300 pm to 400 pm),encompassing any value and subset therebetween. This processing may be performed by, for example, a disk granulator.

[0055] FIG. 2A-2F provide a series of photographs of MOF / polymer composite 140 particles and granules of various sizes, wherein the MOF / polymer composite 140 particles of FIG. 2A range from 0.1 - 2 pm, the MOF / polymer composite 140 particles of FIG. 2B range from 1-53 pm, the MOF / polymer composite 140 particles of FIG. 2C range from 53 - 106 pm, the MOF / polymer composite 140 particles of FIG. 2D range from 106 pm - 125 pm, the MOF / polymer composite 140 particles of FIG. 2E range from 250 - 500 pm, and the MOF / polymer composite 140 particles of FIG. 2F range from 500 - 800 pm. The granules of MOF / polymer composite 140 may be as large as, and including, 10,000 pm.

[0056] In some embodiments, MOF / polymer composite 140 may be synthesized as submicron sized particles between, and including, for example, 250 nm and 500 nm in size (e.g., diameter) (or 250 nm to 375 nm, or 375 nm to 500 nm, or 300 nm to 400 nm), encompassing any value and subset therebetween, which may be too small to be implemented in any traditional column filter device because, under a continuous flow operation, the highly fine powder may be either lost or be converted into a sludge that increases pressure and decreases flow rate along the column bed of the filter. To mitigate this, MOF / polymer composite 140 may be structurally optimized to prevent pressure drops and loss of material during the continuous flow operation using, for example, disc granulation as an agglomeration methodology to make larger particles of MOF / polymer composite 140. For example, disc granulation may convert the fine MOF / polymer particles 140 into larger spherical granules up to, and including, 1,000 pm in diameter by employing a gravity tumble mechanism. A result of the granulation process may be filtered and / or sieved to separate MOF / polymer granules 140 different sizes and / or remove MOF / polymer granules 140 of undesired sizes.

[0057] At times a binder that, on some occasions, may be compatible with the granulation method, may be used to aid in optimized particle size formation (e.g., generate the larger spherical granules) and strength. In some embodiments, a volume (e.g., 1 wt.% to 15 wt.% of the total mass or 1 wt.% to 5 wt.%, or 5 wt.% to 10 wt.%, or 10 wt.% to 15 wt.%, or 1 wt.% to 10 wt.% of the total mass, encompassing any value and subset therebetween) of binder may be incorporated into the MOF / polymer composite 140 by, for example, physical mixing of thematerials via, for example, a mortar and pestle or other incorporation device. In one or more embodiments, the binder may be a polymer (e.g., polyvinyl alcohol, polyvinyl butyral, polyethersulfone, and poly(methyl methacrylate), polyethersulfone, polyvinyl pyrrolidone, polyetherimide, polystyrene, cellulose acetate), polytetrafluoroethylene, polyvinyl formal, starch, an inorganic material (e.g., graphite, alumina, silica), and the like, and any combination thereof.

[0058] The MOF / polymer composite 140 and / or filters including the MOF / polymer composite 140 disclosed herein may be configured for use with large volumes of waste solutions / mixtures and, at times, may be configured for processing large volume streams of waste solutions / mixtures and / or with, or without, continuous flow operations. Exemplary flow rates through the filtration devices disclosed herein (e.g., include, but are not limited to, 100 - 250 mL / min (or 100 mL / min to 150 mL / min, or 150 mL / min to 200 mL / min, or 200 mL / min to 250 mL / min, or 200 mL / min to 300 mL / min), encompassing any value and subset therebetween.

[0059] In one embodiment, the filtration devices disclosed herein (e.g., filter 150) may comprise a cylindrical internal chamber of approximately 2 - 12 inches in height and 0.5 - 7 inches in diameter and / or a length-to-diameter ratio of 2 to 4, encompassing any value and subset therebetween; with at least one input coupling (e.g., inlet port 160) and one output coupling (e.g., outlet port 165). In another embodiment, the filtration devices herein may comprise a cylindrical internal chamber containing a bed of active material (e.g., MOF / polymer composite 140) with length to diameter ratio in the range of 2 to 4. The internal chamber may include a columnar filter housing of approximately 5 grams to 100,000 kilograms (kg) of MOF / polymer composite material (or 5kg to 10,000kg, or 10,000kg to 50,000kg, or 50,000kg to 100,000kg, or 25,000kg to 50,000kg of MOF / polymer composite 140 material), encompassing any value and subset therebetween, packed in, for example, a bed column.

[0060] In some embodiments, an output of the filtration device may be exposed to an electrochemical cell so that metals (e.g., copper) may be extracted (purified) from the waste via electroplating from the leachate. Additionally, or alternatively, a used MOF / polymer composite may be treated (e.g., application of heat (thermal treatment), precipitation treatment, hydrometallurgy methods, vibration, and / or solvents) to remove additional metals therefrom following the filtration process. Thetreated MOF / polymer composite may be thereafter reused in additional filters and / or filtration processes.

[0061] In some embodiments, the systems, devices, compositions, and methods disclosed herein may be used to strip, or extract, metals from solid matrices, such as electronic waste and circuit boards (e.g., WPCBs), solar panel waste, and mining inputs including minerals such as chalcopyrite or enargite, ore, mine tailings, slag, and water mixtures from a given mining operation to generate a metal-containing composition. In some embodiments, a metal-containing composition may be generated by exposing a solid matrix may be exposed to organic chelators / binders, organic oxidizers, and / or other oxidizing agents at neutral, or approximately neutral pH a pH between approximately 0 and 12, a pH between approximately 2 and 10, a pH between approximately 4 and 8, a pH between approximately 5 and 9, a pH between approximately 6 and 8, and a pH of approximately 7, to generate a volume of leachate in which metals and / or compounds from the solid input may be dissolved.

[0062] FIG. 3 provides a flowchart illustrating an exemplary process 300 for extracting metal from a metal-containing composition such as the metal-containing compositions disclosed herein. Process 300 may be performed using, for example, any of the systems, devices, and / or system components disclosed herein.

[0063] Optionally, in step 305, a metal-containing composition may be prepared for processing by, for example, mixing, heating, and / or filtering (e.g., passing the metalcontaining solution, and / or complex water mixture through a mechanical filter to remove dirt or debris). Exemplary metal-containing compositions include, but are not limited to, wastewater, fresh water, ocean water, solutions used to leach metal (e.g., copper, silver, gold into water from electronic waste and / or mining waste), incinerated sewage sludge, and / or any of the aforementioned metal-containing compositions.

[0064] In step 310, the metal-containing composition may be passed through a filter (e.g., filter 150) containing a MOF / polymer composite (e.g., MOF / polymer composite 140) so that metal (e.g., metal ions dissolved in the metal-containing composition) may be captured (e.g., trapped) inside the MOF / polymer composite and / or filtered from the metal-containing composition. In step 315, the MOF / polymer composite with the metal(s) trapped therein (also referred to herein as “metal-enriched MOF / polymer composite”) may be processed to extract the metals. Step 315 may be performed by, for example, exposing the metal-enriched MOF / polymercomposite to one or more chemical and / or mechanical processes including, but not limited to, crushing, grinding, exposure to heat, and / or treatment with a chemical agent such as an acid. In some exemplary embodiments, the metal-enriched MOF / polymer composite may be exposed to high heat (e.g., approximately 440°C) so that the MOF / polymer composite burns off leaving the metal extracted by the MOF / polymer composite behind.

[0065] Optionally, in step 320, the metal-containing composition remaining following execution of step 315 may be further processed to, for example, extract metal therefrom to, for example, purify the metal. Execution of step 320 may include, but is not limited to, exposure to electricity (e.g., electrolysis), mechanical agitation, heating, filtration, etc. In some embodiments, process 300 may be repeated one or more times to fully extract metal from the metal-containing composition.

[0066] FIG. 4 provides a flowchart illustrating an exemplary process 400 for performing process 300 to specifically extract copper and gold from a solid matrix such as electronic waste, scrap, or other post-consumer products (also referred to as "feedstock"). Process 400 may be performed using, for example, any of the systems, devices, and / or system components disclosed herein.

[0067] In step 405, metals may be stripped and / or dissolved (i.e., removed or purified) away from a solid matrix using, for example, a metal-dissolving solution, mechanical agitation (e.g., vibration or scraping), and / or any other acceptable process. Exemplary metal-dissolving solutions may include water, an oxidizing agent, an organic molecule (to help oxidize or bind the metal), an acid, a base, or a combination thereof. Other exemplary metal-dissolving solutions may include water, an oxidizing agent, an organic halide, and / or a chelating and / or binding agent, and any combination thereof, to help solubilize and / or dissolve metal into water and / or a leachate. In some embodiments, the metal-dissolving solution may comprise a combination of one or more inputs including, but not limited to, N-bromosuccinimide (NBS), N-chlorosuccinimide, N-iodosuccinimide, 1,3-Dibromo-5,5-Dimethylhydantoin, pyridine, pyrazine, niacin and their derivatives and the pH of the metal dissolving solution may be approximately 6.5, which is mild compared to the toxic harsh aqua regia and cyanide leaching solutions typically used. When the metal-dissolving solution includes NBS, it may be converted to succinimide during execution of one or more steps of process 400. Additionally, or alternatively, organichalides such as N-Chlorosuccinimide (NCS) may be used instead of NBS. Other additives that can help with leaching efficiency and performance include but are not limited to inorganic salts such as sodium hydroxide, sodium bromide, iron bromide, iron chloride, iron sulfate, and their derivatives.

[0068] FIG. 5A is a block diagram depicting an exemplary manner in which step 405 may be executed to digest and extract metals on / in a solid matrix 510, which in this case is a printed circuit board with a plurality of metallic objects and wires 515 thereon. When solid matrix 510 is exposed to (e.g., submerged in) a metaldissolving solution 550 for a sufficient time to strip the metals therefrom, thereby creating stripped solid matrix 520 with metallic objects and wires 515 dissolved therefrom, possibly leaving behind areas of residue 525 and a metal-enriched leachate 530 containing the metal (in this case, copper and gold) removed from solid matrix 510.

[0069] FIG. 5B provides a diagram showing an exemplary manner in which step 405 may be executed to strip copper (CuO) or (Cu1+) and gold (AuO) from solid matrix 510 by exposing solid matrix 510 to metal-dissolving solution 550 so that the copper and gold may be stripped from solid matrix 510 (thereby creating stripped solid matrix 520) and dissolved into metal-enriched leachate 530 as shown.

[0070] In step 410, the metal-enriched leachate (e.g., metal-enriched leachate 530) may be passed through a filter containing the MOF / polymer composite (e.g., filter 150) so that gold ions or atoms dissolved and / or suspended in the metal-enriched leachate may be selectively trapped inside the MOF / polymer composite and / or filtered from the metal-enriched leachate. That is, the leachate 530 may be collected from the internal chamber through the outlet port of the filter housing. In some embodiments, execution of step 410 reduces the dissolved metal in the leachate to its neutral oxidation state. IN some cases, copper may be unaffected by the execution of step 410 and remain in solution in the metal-enriched leachate as it flows through the MOF / polymer composite filter. In some embodiments, as may be the case when metals are already dissolved in a solution from which they are going to be extracted, step 405 may not be performed and process 400 may begin with step 410. In some embodiments, step 410 may be executed via an adsorptionreduction mechanism provided by, for example, the MOF / polymer composite. This use of an adsorption-reduction mechanism may remove the need to reduce one or more metals (e.g., gold) present in the metal-enriched solution to its neutral state.

[0071] Then, in step 415, gold may be recovered from the MOF / polymer composite filtering device (e.g., filter 150) and purified. Step 415 may be performed via any acceptable means including, but not limited to, mechanical agitation, heating, and / or exposure to solvents. In some embodiments, execution of step 415 includes disassembling the MOF / polymer composite filter, extracting the gold-laden the MOF / polymer composite from the filter, and heating the gold-laden MOF / polymer composite to a temperature (e.g., 400°C) at which the MOF / polymer composite burns off, leaving behind leachate including, for example, gold and iron (a result of burning the MOF / polymer composite). The iron may be separated from the gold via any acceptable process including, for example, an acid wash, so that only gold (e.g., 24K gold) remains.

[0072] In some embodiments, step 415 and / or validation that step 415 was done properly may include characterizing the gold-laden MOF / polymer composite using X-ray diffraction (XRD) and / or X-ray photoelectron spectroscopy (XPS) as shown in, for example, FIGS. 6A and 6B, respectively, wherein it may be seen that the structure of the MOF / polymer composite maintains its crystal structure post filter operation.Further, powder X-ray diffraction (PXRD) confirmed the presence of neutral state gold with diffraction peaks appearing at 38.2°C, 44.4°C, 64.5°C, and 77.6°C. XPS also confirmed the reduction of Au3+ to AuO during the extraction operation. In one experiment, execution of steps 405-415 yielded a concentration of at least 42 wt.% of its weight of gold under a dynamic continuous flow operation, which is 40x higher than the current state-of-the-art, which is activated carbon.

[0073] Optionally, in step 420, copper-infused effluent from the MOF / polymer composite (e.g., the leachate following execution of step 410) is transferred to an electrolytic cell so that copper included therein may be deposited onto a metallic electrode via, for example, an electrochemical plating process, an electrowinning process, an electroextraction process, and / or an electrodeposition process for eventual recovery. FIG. 7A provides a photograph of a volume of copper-infused effluent 710 from the MOF / polymer composite following execution of step 410 before electrochemical purification and FIG. 7B provides a photograph of a volume of copper-depleted effluent 720 from which copper has been extracted after electrochemical purification (e.g., execution of step 720) using electrodes and an electrochemical purification systemO. In one embodiment, PXRD was performed on an electrode used to execute process 420 and the results (shown in the graphs ofFIGs. 7C and 7D) show that Cu2+ is successfully reduced to Cu0 and deposited onto the electrode via the reactions shown in Table 1, provided below. Following execution of step 420, copper may be removed from the electrodes (step 425) for further refinement or processing.TABLE 1

[0074] In some embodiments, high concentrations (e.g., 80-99%) of copper present in the copper-infused effluent may be extracted therefrom over time via execution of step 420. FIG. 7E provides a graph plotting copper concentration in parts per million (ppm) of copper-infused effluent over time during execution of step 420, wherein approximately all copper is extracted from the copper-infused effluent (e.g., copper-infused effluent 710) in approximately two hours, thereby creating copper-depleted effluent (e.g., copper-depleted effluent 720). As copper is cited to account for 10 to 25 percent of metal contents in electronic waste, higher than the content in raw and virgin ores, execution of process 400 provides substantial advantages towards sustainability and cost reductions when compared with traditional ore mining.Additional advantages to execution of step 420 and / or process 400 include use of a metal-dissolving and / or leachate solutions of lower acidity than conventional use of strong acids or aqua regia, which while effective, are too corrosive to be used directly for an electrodeposition process, are toxic to humans and animals, and are environmentally damaging. Execution of process 400 and / or step 420 provides a manner in which to electrodeposit the copper from solution without the use additional chemicals which simplifies the purification process and lowers operation costs all while yielding high quality copper and minimizing waste production.

[0075] Process 400 may be executed once or repeated a plurality (e.g., 2-20) of times with the leachate to ensure all gold and / or copper is extracted therefrom. For example, during a first cycle of executing process 400, 6 - 15 ppm of gold may beextracted from metal-enriched leachate 530, 2 - 5 ppm of gold may be extracted from leachate 530 following a second cycle of executing process 400, and 1 - 3 ppm of gold may be extracted from leachate 530 following a third cycle of executing process 400 with over yields of 50 - 750 mg of gold per 1 kg of e-waste and 5 - 150 g of copper per 1 kg of e-waste. Additionally, or alternatively, process 400 may be executed as a continuous flow operation (in a continuous flow device) or executed in a reactor, both having an inlet and outlet. Exemplary reactors include, but are not limited to, containers, drums (e.g., 50 or 100 gallon drums), and pools configured to hold a volume of, for example, a metal-dissolving solution, a metal-containing composition, a leachate, and / or a source of metal for a period of time to allow one or more methods and / or processes described herein to work (e.g., extract metal from a metal-containing composition). Exemplary continuous flow devices include, but are not limited to, containers, drums (e.g., 50 or 100 gallon drums), and pools configured to allow a volume of, for example, a metal-dissolving solution and / or a leachate to be exposed to and / or flow across a source of metal for a period of time to allow one or more methods and / or processes described herein to work (e.g., extract metal from a metal-containing composition). The reactors and continuous flow devices may have at least one inlet port and one outlet port. Often times, the reactors and / or continuous flow devices may have one or more agitation mechanisms configured to increase movement of the metal-dissolving solution, leachate, metal-containing material (e.g., scrap and / or e-waste chips) In some embodiments, the metaldissolving solution and / or copper-depleted leachate 720 may be recycled and / or reemployed to extract metals from new waste and / or solid matrices including metal.

[0076] FIG. 8 provides a schematic diagram of a system 800 configured to, for example, perform process 300 and / or 400. System 800 includes a waste container 810 configured to hold material comprising waste and metal, such as electronic waste, and / or one or more solid matrices like solid matrix 510 as well as a metaldissolving solution like metal-dissolving solution 550 and / or an aqueous solution of an oxidizing agent and a chelating and / or binding agent. The contents of waste container 810 may be mixed and / or agitated by, for example, a mixer 815 to assist with dissolution of the metal for as long as desired and / or necessary (e.g., approximately ten-twenty-four hours) often times at room temperature. The contents of waste container 810 may then be filtered via a filter 820, which may be a mechanical, magnetic, and / or other type of filter configured to remove, for example,solids, particles, and other materials that may not be dissolved and an output of filter 820 may be a gold-and-copper-enriched leachate like leachate 530. Materials captured by filter 820 may be re-input into waste container 810 for further processing and / or metal extraction as shown. Step 405 of process 400 may be performed in container 810 and / or filter 820.

[0077] Next, when, for example, step 410 is performed, the gold-and-copper-enriched leachate (e.g., leachate 530) may be input into filter 150 for filtration by a MOF / polymer composite like MOF / polymer composite 140. The MOF / polymer composite may remove gold from the gold-and-copper-enriched leachate, thereby generating gold-enriched MOF / polymer composite and copper-enriched leachate (e.g., copper-enriched leachate 710). The gold enriched MOF / polymer composite may be processed via, for example, execution of step 415 to extract a volume of gold 840 therefrom. The copper-enriched leachate 710 may be passed to a copper-enriched leachate container 850 and then to a container 860 in which the copper-enriched leachate may be deposited onto a metallic electrode 865 via, for example, an electrochemical plating process, an electrowinning process, an electroextraction process, and / or an electrodeposition process via, for example, execution of step 420. A volume of copper 870 may then be removed from metallic electrode 865 (step 425) and the process of extracting metal from the solid matrix may be complete. In some embodiments, the leachate remaining after copper extraction may be re-used and / or recycled to, for example, dissolve metals present in additional waste (e.g., repeating step 405).

[0078] In some embodiments, the methods and processes described herein may be used to regenerate the leachate solution after copper and gold are separated and purified. The leachate may be regenerated electrochemically and / or chemically via, for example, the addition of other inputs, heat, and / or electricity. The leachate solution may then be reused to strip out new metals from new solid inputs (e.g., electronic waste, solar cell waste and / or mining inputs that include minerals such as chalcopyrite or enargite, mine tailings, or different solid output from a given mining operation). In some embodiments, the leachate can be continuously regenerated and recycled.

[0079] Embodiments of the present disclosure include:

[0080] Embodiment A: A filter device comprising: a filter housing; an internal mesh chamber; a plurality of porous metal-organic framework / polymer composite particles(MOF / polymer composite particles) disposed within the internal chamber, the plurality of MOF / polymer composite particles comprising: a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites; and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, the active-redox monomers polymerized to form a plurality of active-redox polymers, wherein the plurality of MOF / polymer composite particles capture a metal from a metal-containing composition within the internal chamber.

[0081] Embodiment B: A composition comprising: a plurality of porous metalorganic framework / polymer composite particles (MOF / polymer composite particles), the plurality of MOF / polymer composite particles comprising: a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites; and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, wherein the plurality of MOF / polymer composite particles capture a metal from a metal-containing composition.

[0082] Embodiment C: A method comprising: providing a filter device, the filter device comprising: a filter housing having an inlet port and an outlet port; an internal chamber; a plurality of porous metal-organic framework / polymer composite particles (MOF / polymer composite particles) disposed within the internal chamber, the plurality of MOF / polymer composite particles comprising: a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites; and active-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, the active-redox monomers polymerized to form a plurality of active-redox polymers; flowing a metal-containing composition through the internal chamber into the inlet port and out of the outlet port; and capturing, with the plurality of MOF / polymer composite particles, a metal from the metal-containing composition within the internal chamber.

[0083] Embodiments A, B, and C may have one or more of the following additional elements in any combination:

[0084] Element 1: wherein the filter housing is composed of a polymer, a plastic, a metal, a metal alloy, and any combination thereof.

[0085] Element 2: wherein the internal chamber is composed of stainless steel mesh.

[0086] Element 3: wherein the internal chamber is cylindrical in shape and has a height of 2 inches to 12 inches.

[0087] Element 4: wherein the internal chamber is cylindrical in shape and has a diameter of 0.5 inches to 7 inches.

[0088] Element 5: wherein the internal chamber is cylindrical in shape and has a length to diameter ratio of 2 to 4.

[0089] Element 6: wherein the internal chamber comprises the plurality of MOF / polymer composite particles disposed therein in a volume of 5 grams to 100,000 kilograms.

[0090] Element 7: wherein the active-redox monomers are bound to at least the portion of the plurality of unsaturated open metal coordination sites of the MOF by coordinate covalent bonds.

[0091] Element 8: wherein the MOF is an iron-based MOF and / or a composition of the MOF includes iron ions.

[0092] Element 9: wherein the MOF is an iron sulfate MOF.

[0093] Element 10: wherein the MOF is selected from the group consisting of an MIL-series MOF, a PCN-series MOF, and any combination thereof.

[0094] Element 11: wherein the active-redox monomers are selected from the group consisting of phenylenediamine-based monomers, triarylamine-based monomers, hemin-based monomers, ferrocene-containing monomers, polypyridyl monomers, quinone-based monomers, catechol-functionalized monomers, pyrogallol-based monomers, viologen-based monomers, isomers thereof, comonomers thereof, and any combination thereof.

[0095] Element 12: wherein the active-monomers are selected from the group consisting of p-phenylenediamine; poly(o-phenylenediamine); o-phenylenediamine; m-phenylenediamine; 2-methyl-m-phenylenediamine; 4-methyl-m-phenylenediamine; trimethyl-m-phenylenediamine; N, N'-bis(4-aminophenyl)-N, N'-di(4-methylphenyl)-1,4-phenylenediamine; N, N'-bis(4-methoxyphenyl)-N, N'-bis(4-(4-aminophenyl-4'-methoxyphenylamino)phenyl)-p-phenylenediamine; 4-(bis(4-methylphenyl)amino)benzoic acid; 4-(bis(4-methoxyphenyl)amino)benzoic acid; 1,1'-bis(hydroxymethyl)ferrocene; ferrocenecarboxaldehyde; 2-ferrocene-ethyl-2-oxazoline; 1,1'-bis(phenylphosphine)ferrocene; 2,2'-Bipyridine; ruthenium tris(2, 2'-bipyridine); 2,2':6',2"-terpyridine; 1,10-phenanthroline; quaterpyridine; pyridine-bis(oxazoline); pyridine-oxazoline; p-hydroquinone; disodium 4,5-dihydroxy-1,3-benzenedisulfonate; 2,5-bis((dimethylamino)methyl)benzene-1,4-diol; 2-Methoxy-1,4-hydroquinone; dopamine methacrylamide; 4-vinyl catechol; 3-vinyl catechol; chlorodopamine methacrylamide; N-(prop-2-yn-1-yl)dopamine; 3,4-dihydroxyphenylalanine; N'-(4-vinylbenzyl)-methylviologen; N, N'-dimethyl-4,4'-bipyridinium dicholoride; isomers thereof; co-monomers thereof; and any combination thereof.

[0096] Element 13: wherein the MOF / polymer composite particles have a size of 0.1 micrometers to 10,000 micrometers.

[0097] Element 14: wherein the MOF / polymer composite particles are treated with a binder.

[0098] Element 15: wherein the MOF / polymer composite particles are treated with a binder, the binder selected from the group consisting of a polymer, an inorganic metal, and any combination thereof.

[0099] Element 16: wherein the MOF / polymer composite particles are treated with a polymer binder, the polymer binder selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, polyethersulfone, and poly(methyl methacrylate), polyethersulfone, polyvinyl pyrrolidone, polyetherimide, polystyrene, cellulose acetate, polytetrafluoroethylene, polyvinyl formal, starch, and any combination thereof.

[0100] Element 17: wherein the MOF / polymer composite particles are treated with an inorganic metal binder, the inorganic metal binder selected from the group consisting of graphite, alumina, silica, and any combination thereof.

[0101] Element 18: wherein the metal-containing composition is selected from the group consisting of tap water, wastewater, sea water, wastewater from electronic waste, electronic waste, solar cell waste,, evaporator scrap waste, mining waste, refining waste, minerals, ores, mine tailings, slag, ash, fly ash, dust, trash, photographic film waste, medical film waste, jewelry waste, dental waste, sewage sludge, industrial by-product waste, and any combination thereof.

[0102] Element 19: wherein flowing the metal-containing composition through the internal chamber at a continuous flow rate.

[0103] Element 20: wherein flowing the metal-containing composition through the internal chamber at a continuous flow rate of 100 milliliters per minute to 2000 milliliters per minute.

[0104] Element 21: wherein the flowing and the capturing is performed at a pH between 0 and 12.

[0105] Element 22: wherein the flowing and the capturing is performed at or near room temperature.

[0106] Element 23: wherein the flowing and the capturing is performed at or near ambient pressure.

[0107] Element 24: further comprising: stripping the captured metal from MOF / polymer composite particles within the internal chamber, thereby resulting in a leachate; and collecting the leachate through the outlet port.

[0108] Element 25: further comprising: stripping the captured metal from MOF / polymer composite particles within the internal chamber, thereby resulting in a leachate, wherein the stripping is performed using a metal-dissolving solution; and collecting the leachate through the outlet port.

[0109] Element 26: further comprising: stripping the captured metal from MOF / polymer composite particles within the internal chamber, thereby resulting in a leachate, wherein the stripping is performed using a metal-dissolving solution, the metal-dissolving solution selected from the group consisting of an oxidizing agent, an organic halide, a chelating agent, a binding agent, and any combination thereof; and collecting the leachate through the outlet port.

[0110] Element 27: further comprising: stripping the captured metal from MOF / polymer composite particles within the internal chamber, thereby resulting in a leachate, wherein the stripping is performed using a metal-dissolving solution, the metal-dissolving solution selected from the group consisting of N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, 1,3-Dibromo-5,5-Dimethylhydantoin, pyridine, pyrazine, niacin, derivatives thereof, and any combination thereof; and collecting the leachate through the outlet port.

[0111] Element 28: further comprising: stripping the captured metal from MOF / polymer composite particles within the internal chamber, thereby resulting in a leachate, wherein the stripping is performed using mechanical agitation; and collecting the leachate through the outlet port.

[0112] Element 29: further comprising: stripping the captured metal from MOF / polymer composite particles within the internal chamber, thereby resulting in a leachate, wherein the stripping is performed using mechanical agitation, the mechanical agitation selected from the group consisting of mechanical vibration,mechanical scraping, and any combination thereof; and collecting the leachate through the outlet port.

[0113] By way of non-limiting example, exemplary combinations applicable to Embodiment A include: any non-limiting combination of one, more, or all of Elements 1-18.

[0114] By way of non-limiting example, exemplary combinations applicable to Embodiment B include: any non-limiting combination of one, more, or all of Elements 7-18.

[0115] By way of non-limiting example, exemplary combinations applicable to Embodiment C include: any non-limiting combination of one, more, or all of Elements 1-29.

[0116] The terminology used in this disclosure is intended solely to describe specific embodiments and should not be interpreted as limiting the scope of the disclosure. For instance, unless clearly stated otherwise, singular terms such as “a,” “an,” and “the” should be understood to include their plural counterparts.Additionally, terms like “contains,” “containing,” “includes,” “including,” “comprises,” “comprising,” and similar expressions indicate the presence of certain features, numbers, steps, operations, elements, or components, but do not exclude the possibility of additional or alternative features, steps, or components. As used herein, the term “approximately” or "about" or "near" with reference to a numerical value can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range.

[0117] Directional or orientation terms used herein are provided only for reference and should not be seen as limiting. However, it is acknowledged that such terms may relate to the position of a user or operator. Therefore, no restrictions should be inferred from their usage. Furthermore, ordinal terms such as “first,” “second,” or “third” are used solely to distinguish elements and do not imply any sequence or required quantity. For example, referencing a “third” component does not necessitate the existence of a “first” or “second.” Additionally, the terms “coupled,” “connected,” or “attached,” whether used with or without “to,” may refer to either direct or indirect connections unless explicitly stated otherwise.

[0118] Although several exemplary embodiments have been described, those skilled in the art will recognize that substitutions, changes, and modifications can be made without departing from the scope and spirit of the disclosure. The describedembodiments are not intended to be limiting or to represent the only way to implement the disclosure. Rather, the disclosure is meant to encompass all alternatives and equivalents that fall within the scope of the appended claims.Furthermore, when the claims refer to an apparatus, system, or component as being “adapted to,” “configured to,” “enabled to,” or similar phrases with regard to performing a function, such language covers the ability of that element to perform the function — even if the function is not currently active, in use, or enabled.

Claims

CLAIMS:What is claimed is:

1. A device comprising:a chamber with a cavity, an inlet port, and an outlet port; anda plurality of porous metal-organic framework / polymer composite (MOF / polymer composite) particles disposed within the cavity, the plurality of MOF / polymer composite particles comprising:a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites; andactive-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, the active-redox monomers polymerized to form a plurality of active-redox polymers, wherein the plurality of MOF / polymer composite particles are configured to capture or react to a metal of a metal-containing composition disposed within the chamber.

2. The device of claim 1, wherein the device at least one of a continuous flow device and a reactor.

3. The device of claim 1 or 2, wherein the chamber comprises at least one of a polymer, a plastic, a metal, a metal alloy, and any combination thereof.

4. The device of any of the above claims, wherein the plurality of MOF / polymer composite particles disposed in the cavity has a volume of 5 grams to 100,000 kilograms.

5. The device of any of the above claims, wherein the active-redox monomers are bound to at least the portion of the plurality of unsaturated open metal coordination sites of the MOF.

6. The device of any of the above claims, wherein the composition of the MOF includes iron ions.

7. The device of any of the above claims, wherein the MOF is selected from the group consisting of an MIL-series MOF, a PCN-series MOF, and any combination thereof.

8. The device of any of the above claims, wherein the active-redox monomers are selected from the group consisting of phenylenediamine-based monomers, triarylamine-based monomers, hemin-based monomers, ferrocene-containing monomers, polypyridyl monomers, quinone-based monomers, catechol-functionalized monomers, pyrogallol-based monomers, viologen-based monomers, isomers thereof, co-monomers thereof, and any combination thereof.

9. The device of any of the above claims, wherein the active-monomers are selected from the group consisting of p-phenylenediamine; o-phenylenediamine, m-phenylenediamine; 2-methyl-m-phenylenediamine; 4-methyl-m-phenylenediamine; trimethyl-m-phenylenediamine; N, N'-bis(4-aminophenyl)-N, N'-di(4-methylphenyl)-1,4-phenylenediamine; N, N'-bis(4-methoxyphenyl)-N, N'-bis(4-(4-aminophenyl-4'-methoxyphenylamino)phenyl)-p-phenylenediamine; 4-(bis(4-methylphenyl)amino)benzoic acid; 4-(bis(4-methoxyphenyl)amino)benzoic acid; 1,1'-bis(hydroxymethyl)ferrocene; ferrocenecarboxaldehyde; 2-ferrocene-ethyl-2-oxazoline; 1,1'-bis(phenylphosphine)ferrocene; 2,2'-Bipyridine; ruthenium tris(2, 2'-bipyridine); 2,2':6',2"-terpyridine; 1,10-phenanthroline; quaterpyridine; pyridine-bis(oxazoline); pyridine-oxazoline; p-hydroquinone; disodium 4,5-dihydroxy-1,3-benzenedisulfonate; 2,5-bis((dimethylamino)methyl)benzene-1,4-diol; 2-Methoxy-1,4-hydroquinone; dopamine methacrylamide; 4-vinyl catechol; 3-vinyl catechol; chlorodopamine methacrylamide; N-(prop-2-yn-1-yl)dopamine; 3,4-dihydroxyphenylalanine; N'-(4-vinylbenzyl)-methylviologen; N, N'-dimethyl-4,4'-bipyridinium dicholoride; isomers thereof; co-monomers thereof; and any combination thereof.

10. The device of any of the above claims, wherein the MOF / polymer composite particles have a size of 0.1 micrometers to 10,000 micrometers.

11. The device of any of the above claims, wherein the plurality of MOF / polymer composite particles are treated with a binder.

12. The device of claim 11, wherein the binder selected from the group consisting of a polymer, an inorganic metal, and any combination thereof.

13. The device of any of the above claims, wherein the MOF / polymer composite particles are treated with a polymer binder, the polymer binder selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, polyethersulfone, and poly(methyl methacrylate), polyethersulfone, polyvinyl pyrrolidone, polyetherimide, polystyrene, cellulose acetate, polytetrafluoroethylene, polyvinyl formal, starch, and any combination thereof.

14. The device of any of the above claims, wherein the MOF / polymer composite particles are treated with an inorganic metal binder, the inorganic metal binderselected from the group consisting of graphite, alumina, silica, and any combination thereof.

15. The device of any of the above claims, wherein the metal-containing composition is selected from the group consisting of water, tap water, wastewater, sea water, wastewater from electronic waste, electronic waste, solar cell waste, evaporator scrap waste, mining waste, refining waste, minerals, ores, mine tailings, slag, ash, fly ash, dust, trash, photographic film waste, medical film waste, jewelry waste, dental waste, sewage sludge, industrial by-product waste, and any combination thereof.

16. The device of any of the above claims, wherein the metal is a transition metal, a rare earth metal, a platinum group metal, a precious metal, and a combination thereof.

17. The device of any of the above claims, wherein the metal-containing composition is selected from the group consisting of an oxidizing agent, an organic halide, an inorganic halide, a chelating agent, a binding agent, an acid, a base, and any combination thereof.

18. The device of any of the above claims, wherein the metal-containing composition is selected from the group consisting of N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, 1,3-Dibromo-5,5-Dimethylhydantoin, pyridine, pyrazine, niacin, nicotinic acid, derivatives thereof, and any combination thereof.

19. A composition comprising:a plurality of porous metal-organic framework / polymer composite particles (MOF / polymer composite particles), the plurality of MOF / polymer composite particles comprising:a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites; andactive-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF,wherein the plurality of MOF / polymer composite particles capture or react to a metal of a metal-containing composition.

20. The composition of claim 19, wherein the active-redox monomers are bound to at least the portion of the plurality of unsaturated open metal coordination sites of the MOF by coordinate covalent bonds.

21. The composition of claim 19 or 20, wherein the MOF is an iron-based MOF.

22. The composition of any of claims 19-21, wherein the MOF is selected from the group consisting of an MIL-series MOF, a PCN-series MOF, and any combination thereof.

23. The composition of any of claims 19-22, wherein the active-redox monomers are selected from the group consisting of phenylenediamine-based monomers, triarylamine-based monomers, hemin-based monomers, ferrocene-containing monomers, polypyridyl monomers, quinone-based monomers, catechol-functionalized monomers, pyrogallol-based monomers, viologen-based monomers, isomers thereof, co-monomers thereof, and any combination thereof.

24. The composition of any of claims 19-23, wherein the active-monomers are selected from the group consisting of p-phenylenediamine; poly(o-phenylenediamine); o-phenylenediamine; m-phenylenediamine; 2-methyl-m-phenylenediamine; 4-methyl-m-phenylenediamine; trimethyl-m-phenylenediamine; N, N'-bis(4-aminophenyl)-N, N'-di(4-methylphenyl)-1,4-phenylenediamine; N, N'-bis(4-methoxyphenyl)-N, N'-bis(4-(4-aminophenyl-4'-methoxyphenylamino)phenyl)-p-phenylenediamine; 4-(bis(4-methylphenyl)amino)benzoic acid; 4-(bis(4-methoxyphenyl)amino)benzoic acid; 1,1'-bis(hydroxymethyl)ferrocene; ferrocenecarboxaldehyde; 2-ferrocene-ethyl-2-oxazoline; 1,1'-bis(phenylphosphine)ferrocene; 2,2'-Bipyridine; ruthenium tris(2,2'-bipyridine);2,2':6',2"-terpyridine; 1,10-phenanthroline; quaterpyridine; pyridine-bis(oxazoline); pyridine-oxazoline; p-hydroquinone; disodium 4,5-dihydroxy-1,3-benzenedisulfonate; 2,5-bis((dimethylamino)methyl)benzene-1,4-diol; 2-Methoxy-1,4-hydroquinone; dopamine methacrylamide; 4-vinyl catechol; 3-vinyl catechol; chlorodopamine methacrylamide; N-(prop-2-yn-1-yl)dopamine; 3,4-dihydroxyphenylalanine; N'-(4-vinylbenzyl)-methylviologen; N, N'-dimethyl-4,4'-bipyridinium dicholoride; isomers thereof; co-monomers thereof; and any combination thereof.

25. The composition of any of claims 19-24, wherein the MOF / polymer composite particles have a size of 0.1 micrometers to 10,000 micrometers.

26. The composition of any of claims 19-25, wherein the MOF / polymer composite particles are treated with a binder.

27. The composition of any of claims 19-26, wherein the MOF / polymer composite particles are treated with a binder, the binder selected from the group consisting of a polymer, an inorganic metal, and any combination thereof.

28. The composition of any of claims 19-27, wherein the MOF / polymer composite particles are treated with a polymer binder, the polymer binder selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, polyethersulfone, and poly(methyl methacrylate), polyethersulfone, polyvinyl pyrrolidone, polyetherimide, polystyrene, cellulose acetate, polytetrafluoroethylene, polyvinyl formal, starch, and any combination thereof.

29. The composition of any of claims 19-28, wherein the MOF / polymer composite particles are treated with an inorganic metal binder, the inorganic metal binder selected from the group consisting of graphite, alumina, silica, and any combination thereof.

30. The composition of any of claims 19-29, wherein the metal-containing composition is selected from the group consisting of tap water, wastewater, sea water, wastewater from electronic waste, electronic waste, solar cell waste, evaporator scrap waste, mining waste, refining waste, minerals, ores, mine tailings, slag, ash, fly ash, dust, trash, photographic film waste, medical film waste, jewelry waste, dental waste, sewage sludge, industrial by-product waste, and any combination thereof.

31. A method comprising:providing a continuous flow device or reactor, the continuous flow device or reactor comprising:an internal chamber having a cavity, an inlet port, and an outlet port; a plurality of porous metal-organic framework / polymer composite particles (MOF / polymer composite particles) disposed within the internal chamber, the plurality of MOF / polymer composite particles comprising:a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites; andactive-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, the active-redox monomers polymerized to form a plurality of active-redox polymers; flowing a metal-containing composition into the cavity via the inlet port and out of the cavity via the outlet port; andcapturing, with the plurality of MOF / polymer composite particles, a metal from the metal-containing composition within the internal chamber.

32. The method of claim 31, wherein flowing the metal-containing composition through the internal chamber at a continuous flow rate.

33. The method of claim 31 or 32, wherein flowing the metal-containing composition through the internal chamber at a continuous flow rate of 100 milliliters per minute to 2000 milliliters per minute.

34. The method of any of claims 31 -33, wherein the flowing and the capturing is performed at a pH between approximately 0 and 12, a pH between approximately 2 and 10, a pH between approximately 4 and 8, a pH between approximately 5 and 9, a pH between approximately 6 and 8, and a pH of approximately 7.

35. A filter device comprising:a filter housing;an internal mesh chamber;a plurality of porous metal-organic framework / polymer composite (MOF / polymer composite) particles disposed within the internal mesh chamber, the plurality of MOF / polymer composite particles comprising:a porous metal-organic framework (MOF) with a plurality of unsaturated open metal coordination sites; andactive-redox monomers bound to at least a portion of the plurality of unsaturated open metal coordination sites of the MOF, the active-redox monomers polymerized to form a plurality of active-redox polymers, wherein the plurality of MOF / polymer composite particles are configured to capture a metal from a metal-containing composition within the internal mesh chamber.

36. The filter device of claim 35, wherein the filter housing comprises at least one of a polymer, a plastic, a metal, a metal alloy, and any combination thereof.

37. The filter device of claim 35 or 36, wherein the internal mesh chamber comprises a stainless steel mesh.

38. The filter device of claim 35, 36, or 37 wherein the internal mesh chamber is cylindrical in shape and has a height of 2 inches to 12 inches.

39. The filter device of any of claims 35-38, wherein the internal mesh chamber is cylindrical in shape and has a diameter of 0.5 inches to 7 inches.

40. The filter device of any of claims 35-39, wherein the internal mesh chamber is cylindrical in shape and has a length to diameter ratio of 2 to 4.

41. The filter device of any of claims 35-40, wherein the internal mesh chamber houses the plurality of MOF / polymer composite particles disposed therein in a volume of 5 grams to 100,000 grams.

42. The filter device of any of claims 35-41, wherein the active-redox monomers are bound to at least the portion of the plurality of unsaturated open metal coordination sites of the MOF by coordinate covalent bonds.

43. The filter device of any of claims 35-42, wherein the composition of the MOF includes iron ions.

44. The filter device of any of claims 35-42, wherein the MOF is an iron sulfate MOF.

45. The filter device of any of claims 35-44, wherein the MOF is selected from the group consisting of an MIL-series MOF, a PCN-series MOF, and any combination thereof.

46. The filter device of any of claims 35-45, wherein the active-redox monomers are selected from the group consisting of phenylenediamine-based monomers, triarylamine-based monomers, hemin-based monomers, ferrocene-containing monomers, polypyridyl monomers, quinone-based monomers, catechol-functionalized monomers, pyrogallol-based monomers, viologen-based monomers, isomers thereof, co-monomers thereof, and any combination thereof.

47. The filter device of any of claims 35-46, wherein the active-monomers are selected from the group consisting of p-phenylenediamine; poly(o-phenylenediamine); o-phenylenediamine; m-phenylenediamine; 2-methyl-m-phenylenediamine; 4-methyl-m-phenylenediamine; trimethyl-m-phenylenediamine; N, N'-bis(4-aminophenyl)-N, N'-di(4-methylphenyl)-1,4-phenylenediamine; N, N'-bis(4-methoxyphenyl)-N, N'-bis(4-(4-aminophenyl-4'-methoxyphenylamino)phenyl)-p-phenylenediamine; 4-(bis(4-methylphenyl)amino)benzoic acid; 4-(bis(4-methoxyphenyl)amino)benzoic acid; 1,1'-bis(hydroxymethyl)ferrocene; ferrocenecarboxaldehyde; 2-ferrocene-ethyl-2-oxazoline; 1,1'-bis(phenylphosphine)ferrocene; 2,2'-Bipyridine; ruthenium tris(2,2'-bipyridine);2,2':6',2"-terpyridine; 1,10-phenanthroline; quaterpyridine; pyridine-bis(oxazoline); pyridine-oxazoline; p-hydroquinone; disodium 4,5-dihydroxy-1,3-benzenedisulfonate; 2,5-bis((dimethylamino)methyl)benzene-1,4-diol; 2-Methoxy-1,4-hydroquinone; dopamine methacrylamide; 4-vinyl catechol; 3-vinyl catechol; chlorodopamine methacrylamide; N-(prop-2-yn-1-yl)dopamine; 3,4-dihydroxyphenylalanine; N'-(4-vinylbenzyl)-methylviologen; N, N'-dimethyl-4,4'-bipyridinium dicholoride; isomers thereof; co-monomers thereof; and any combination thereof.

48. The filter device of any of claims 35-47, wherein the MOF / polymer composite particles have a size of 0.1 micrometers to 10,000 micrometers.

49. The filter device of any of claims 35-48, wherein the MOF / polymer composite particles are treated with a binder.

50. The filter device of claim 49, wherein the binder selected from the group consisting of a polymer, an inorganic metal, and any combination thereof.

51. The filter device of any of claims 35-50, wherein the MOF / polymer composite particles are treated with a polymer binder, the polymer binder selected from the group consisting of polyvinyl alcohol, polyvinyl butyral, polyethersulfone, and poly(methyl methacrylate), polyethersulfone, polyvinyl pyrrolidone, polyetherimide, polystyrene, cellulose acetate, polytetrafluoroethylene, polyvinyl formal, starch, and any combination thereof.

52. The filter device of any of claims 35-51, wherein the MOF / polymer composite particles are treated with an inorganic metal binder, the inorganic metal binder selected from the group consisting of graphite, alumina, silica, and any combination thereof.

53. The filter device of any of claims 35-52, wherein the metal-containing composition is selected from the group consisting of tap water, wastewater, sea water, wastewater from electronic waste, electronic waste, solar cell waste, mining waste, refining waste, minerals, ores, mine tailings, slag, ash, fly ash, dust, trash, photographic film waste, medical film waste, jewelry waste, dental waste, sewage sludge, industrial by-product waste, and any combination thereof.

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