# US 2026/0209979 A1 · Recovery of energy critical high value metals using functionalized materials

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- Number: US 2026/0209979 A1
- Document ID: US20260209979A1
- Status: Published application
- Kind: A1
- Application number: 19/126,807
- Filed: 2023-11-03
- Published: 2026-07-23
- Earliest claimed: 2022-11-03
- Assignees: Cornell University
- Applicants: Cornell University
- Inventors: Greeshma GADIKOTA; Ruyi ZHENG; Prince OCHONMA; Tianhe YIN; Sohaib MOHAMMED; Hassnain ASGAR; Dhruvi PATEL; Peilong LU
- Web page: https://patentgrep.com/patent/US20260209979A1

## CPC

- C25B 1/20: Hydroxides
- C25C 1/20: of noble metals
- B01J 20/3204: {Inorganic carriers, supports or substrates}
- B01J 20/3219: {involving a particular spacer or linking group, e.g. for attaching an active group}
- B01J 20/3253: {comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures}
- B01J 20/3265: {with an organic functional group containing a metal, e.g. a metal affinity ligand}
- B01J 20/3293: {Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers}
- B01J 20/3433: {of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425}
- B01J 20/3475: {in the liquid phase}
- C22B 3/045: {Leaching using electrochemical processes}
- C22B 3/24: by adsorption on solid substances, e.g. by extraction with solid resins
- C22B 3/42: by ion-exchange extraction
- C22B 3/44: by chemical processes (treatment or purification of solutions by liquid-liquid extraction C22B3/26, by ion-exchange extraction C22B3/42)
- C22B 11/04: {by wet processes (extraction of metal compounds by leaching in organic solutions C22B3/16; treatment or purification of solutions by liquid-liquid extraction C22B3/26)}
- C22B 15/0089: {by chemical methods}
- C22B 19/26: {Refining solutions containing zinc values, e.g. obtained by leaching zinc ores (treatment or purification of solutions by liquid-liquid extraction, by ion exchange or by adsorption C22B3/00)}
- C22B 23/0461: {by chemical methods}
- C22B 59/00: Obtaining rare earth metals
- C25B 1/01: Products
- C25B 9/19: with diaphragms
- Y02P 10/20: Recycling
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- C25C: PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Provided are methods for the capture of energy critical high value metals and an apparatus or system for an electrochemical approach to produce Ca- and Mg-hydroxides, silica, and leach metals into the solution phase that can be sequentially recovered. The methods entail: providing a functionalized sorbent for metal capture; recovering the metal from the metal-containing solution by contacting the functionalized sorbent with the metal-containing solution, thereby adsorbing metal ions from the metal-containing solution onto the functionalized sorbent; and desorbing the metal ions from the functionalized sorbent by contacting the functionalized sorbent with a stripping agent, thereby forming a stripped solution containing the metal ions.

## Claims

### Claim at position 1

1-47. (canceled)

### Claim 48

A method of producing one or more metal hydroxide, oxide, and/or carbonate compounds and/or recovering one or more metals comprising:
providing an apparatus comprising an anode, a cathode, a liquid electrolyte, and optionally a separator membrane between the anode and the cathode:
providing one or more precursor compounds comprising one or more metal-bearing materials wherein the one or more precursor compounds are substantially insoluble in the liquid electrolyte and located in a first location;
applying a voltage between the anode and the cathode;
dissolving at least part of the one or more precursor compounds to form one or more soluble metal ions diffused in at least part of the liquid electrolyte as a metal-containing solution; and
accumulating one or more metal hydroxide, oxide, and/or carbonate compounds substantially in a second location different from the first location, wherein the one or more metal hydroxide, oxide, and/or carbonate compounds are substantially insoluble in water or in the liquid electrolyte.

### Claim 49 (depends on 48)

The method of claim 48, wherein the apparatus comprises:
a first chamber comprising the anode;
a second chamber comprising the cathode;
a conduit connecting the first chamber and the second chamber; and
optionally a separator placed in the conduit;
wherein the liquid electrolyte comprising a solvent and optionally one or more additives;
wherein the one or more metal-bearing siliceous materials are positioned inside the first chamber and optionally close to the anode, wherein at least part of the one or more metal-bearing siliceous materials are dissolved in the solvent under the applied voltage for a time period by reacting with the H+ in the first chamber generated at or close to the anode; and
wherein the one or more metal hydroxides, oxides, or carbonates, are accumulated substantially in the lower half of the conduit and/or in the lower half of the second chamber by reacting the soluble metal ion(s) with the OH− diffused to the conduit from the second chamber wherein the OH− is generated at or close to the cathode under the applied voltage by electrochemical reaction(s).

### Claim 50 (depends on 48)

The method of claim 48, wherein dissolving at least part of the one or more precursor compounds comprise one or more reactions of:
i. M1x1M2x2M3x3SiOy+n1 H+→a1 M1b1++a2 M2b2++a3 M3b3++n2 SiO2+n3 H2O, wherein 0≤x1≤4, 0≤x2≤4, 0≤x3≤4, 1≤y≤8, x1+x2+x3>0, a1+a2+a3>0, b1≥1, b2≥1, b3≥1, n1>0, n2>0, and n3>0;
ii. M1x1M2x2M3x3Oy+n1 H+→a1 M1b1++a2 M2b2++a3 M3b3++n2 O2+n3 H2O, wherein 0≤x1≤4, 0≤x2≤4, 0≤x3≤4, 1≤y≤8, x1+x2+x3>0, a1+a2+a3>0, b1≥1, b2≥1, b3≥1, n1>0, n2>0, and n3>0;
iii. M1x1M2x2M3x3Alx4Six5Oy+n1 H+→a1 M1b1++a2 M2b2++a3 M3b3++n2 SiO2+n4 Al2O3+n3 H2O, wherein 0≤x1≤4, 0≤x2≤4, 0≤x3≤4, 0≤x4≤4, 0≤x5≤4, 1≤y≤8, x1+x2+x3>0, a1+a2+a3>0, b1≥1, b2≥1, b3≥1, n1>0, n2>0, n3>0, and n4>0; and/or
iv. M1x1M2x2M3x3(OH)y+n1 H+→a1 M1b1++a2 M2b2++a3 M3b3++n2 (OH)y+n3 H2O, wherein 0≤x1≤4, 0≤x2≤4, 0≤x3≤4, 1≤y≤8, x1+x2+x3>0, a1+a2+a3>0, b1≥1, b2≥1, b3≥1, n1>0, n2>0, and n3>0.

### Claim 51

(canceled)

### Claim 52 (depends on 50)

The method of claim 50, wherein each of M1, M2, and M3 are independently selected from Ca, Mg, Al, Fe, Mn, Pb, Ni, Co, Zn, Cu, Mo, Pt, Pd, Rh, Ru, Ir, Os, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Y.

### Claim at position 7

53-55. (canceled)

### Claim 56 (depends on 48)

The method of claim 48, wherein the one or more precursor compounds comprise steel slag, minerals, mine-tailings, industrial residues, rocks, fly ash, ores, or brine with dissolved solids, and/or wherein the one or more precursor compounds comprise one or more metal-bearing siliceous materials selected from wollastonite, enstatite, olivine, basalt, serpentine, pyroxene, diopside, feldspar, mica, talc, sulfide ores, or gypsum, or is composed of or derived from rocks or ores containing one or more of metal silicates.

### Claim at position 9

57-58. (canceled)

### Claim 59 (depends on 48)

The method of claim 48, wherein the anode is at least partially submerged in the electrolyte and configured to generate acid; and wherein the cathode is at least partially submerged in the electrolyte and configured to generate hydroxyl ions.

### Claim 60

(canceled)

### Claim 61 (depends on 49)

The method of claim 49, wherein the conduit has a pH gradience from a first pH value that is acidic to a second pH value that is basic.

### Claim at position 13

62-63. (canceled)

### Claim 64 (depends on 48)

The method of claim 48, further comprising:
introducing a gas stream comprising carbon dioxide;
absorbing at least part of the carbon dioxide by reacting the carbon dioxide with the one or more metal hydroxides or oxides to form one or more metal carbonates.

### Claim 65 (depends on 48)

The method of claim 48, wherein the first location and the second location are separated by at least one filter or membrane or at least one porous material.

### Claim 66

(canceled)

### Claim 67 (depends on 48)

The method of claim 48, further comprising:
providing a functionalized sorbent for metal capture;
capturing the metal from the metal-containing solution onto the functionalized sorbent at a negative potential; and
releasing the metal from the functionalized sorbent at a positive potential, thereby regenerating the working electrode.

### Claim 68 (depends on 67)

The method of claim 67, wherein the functionalized sorbent comprises:
a substrate;
a redox active ligand; and
optionally a linker;
wherein the ligand is directly attached to the substrate or tethered to the substrate via the linker.

### Claim at position 19

69-70. (canceled)

### Claim 71 (depends on 68)

The method of claim 68, wherein the ligand is selected from Nile Blue (NB), 3,4-Dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid (Alizarin Red S; ARS), and vinyl-ferrocene (VF).

### Claim 72 (depends on 68)

The method of claim 68, wherein the linker is selected from 3-(2-aminoethylamino) propyltrimethoxysilane (A2), 3-(aminopropyl)triethoxy silane (AEPTS), and 3-mercaptopropyl trimethoxysilane (M).

### Claim at position 22

73-77. (canceled)

### Claim 78 (depends on 48)

The method of claim 48, further comprising:
providing a functionalized sorbent for metal capture;
recovering the metal from the metal-containing solution by contacting the functionalized sorbent with the metal-containing solution, thereby adsorbing metal ions from the metal-containing solution onto the functionalized sorbent, wherein the functionalized sorbent comprising an electroactive surface having one or more ligands tethered thereon, said surface being, due to the one or more ligands, highly selective for electrochemical adsorption and/or desorption from metal bearing solutions; and
desorbing the metal ions from the functionalized sorbent by contacting the functionalized sorbent with a stripping agent, thereby forming a stripped solution containing the metal ions.

### Claim 79 (depends on 78)

The method of claim 78, wherein the one or more ligands are highly selective for electrochemical adsorption and/or desorption of one or more metals selected from Pt, Pd, Ni, Mn, Co, Cu, Ag, Fe, La, Ce, or any combinations thereof.

### Claim 80 (depends on 78)

The method of claim 78, wherein the functionalized sorbent comprises Si-M-VIL of formula:

### Claim 81 (depends on 80)

The method of claim 80, wherein the ligand of the functionalized sorbent is highly selective for electrochemical adsorption and/or desorption of platinum for recovering platinum from the metal-containing solution.

### Claim 82 (depends on 48)

The method of claim 48, wherein the apparatus comprises:
a first chamber comprising an anode;
a second chamber comprising a cathode;
a conduit connecting the first chamber and the second chamber;
optionally a separator configured to separate the anode and cathode;
an electrolyte comprising a solvent and optionally one or more additives; and
one or more metal-bearing siliceous materials positioned inside the first chamber and optionally close to the anode, wherein at least part of the one or more metal-bearing siliceous materials are dissolved in the solvent/electrolyte, and one or more products are produced under an applied voltage for a time period, wherein the one or more products are selected from one or more metal hydroxides, silica, one or more metal ion dissolved in the solvent/electrolyte, hydrogen, oxygen, optionally one or more metal carbonates, optionally one or more metal oxides, or any combination thereof.

### Claim 83 (depends on 82)

The method of claim 82, further comprising:
a first filter or membrane positioned between the first chamber and a first end of the conduit; and
optionally a second filter or membrane positioned between the second chamber and a second end of the conduit,
wherein the first filter or membrane is configured to prevent the one or more metal-bearing siliceous materials from diffusing to the conduit from the first chamber and wherein the second filter or membrane is configured to prevent the one or more products from diffusing to the second chamber from the conduit.

### Claim 84 (depends on 82)

The method of claim 82, wherein four or more products are produced comprising:
one or more metal hydroxides accumulated substantially on the lower half of the conduit;
a silica material accumulated substantially on the lower half of the first chamber;
oxygen accumulated substantially at the upper half of the first chamber;
hydrogen accumulated substantially at the upper half of the second chamber;
optionally one or more dissolved metal ions primarily concentrated in the first chamber converted from the one or more metal-bearing siliceous materials wherein the concentrated metal is selected from Ca, Mg, Al, and Fe; and
optionally one or more metal carbonates, hydroxides, and/or oxides accumulated substantially on the lower half of the conduit or on the lower half of the second chamber, wherein the metal of the metal carbonates, hydroxides, and/or oxides, is selected from Mn, Pb, Ni, Co, Zn, Cu, Mo, Pt, Pd, Rh, Ru, Ir, Os, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and Y.