Reactive electrochemical membrane for wastewater treatment

Abstract

Aspects of the invention include a porous and water-permeable electrode for electrocatalysis comprising: a porous and water-permeable reactive electrochemical membrane (“REM”) comprising: a porous and water-permeable support membrane; wherein the support membrane comprises a titanium metal; and an electrocatalytic coating on at least a portion of the metal support membrane, the electrocatalytic coating being a tin oxide bilayer comprising: a first layer adjacent to and directly contacting the metal support membrane; wherein the first layer comprises tin oxide doped with antimony; and a second layer adjacent to and directly contacting the first layer; wherein the second layer forms a surface of the REM such that the second layer is in direct contact with an aqueous solution when the REM is in contact with the aqueous solution; wherein the second layer comprises tin oxide doped with antimony and nickel or cerium. Preferably, the support membrane is formed of a titanium metal.

Claims

1. A porous and water-permeable electrode for electrocatalysis comprising: a porous and water-permeable reactive electrochemical membrane (“REM”) comprising: a porous and water-permeable support membrane; wherein the support membrane is formed of a titanium metal; and an electrocatalytic coating on at least a portion of the metal support membrane, the electrocatalytic coating being a tin oxide bilayer comprising: a first layer adjacent to and directly contacting the metal support membrane; wherein the first layer comprises tin oxide doped with antimony; and a second layer adjacent to and directly contacting the first layer; wherein the second layer forms a surface of the REM such that the second layer is in direct contact with an aqueous solution when the REM is in contact with the aqueous solution; wherein the second layer comprises tin oxide doped with antimony and nickel or cerium, wherein a composition of the first layer is characterized by formula FX2:
Sb.sub.xSn.sub.1-xO.sub.2  (FX2); wherein x is greater than or equal to 0.1 and less than or equal to 0.5.

2. The electrode of claim 1, wherein a composition of the first layer comprises 3 at. % to 17 at. % of antimony.

3. The electrode of claim 1, wherein a composition of the second layer comprises 0.3 at. % to 1.7 at. % of antimony and (i) 0.3 at. % to 1.7 at. % of nickel or (ii) 0.3 at. % to 1.7 at. % of cerium.

4. The electrode of claim 1, wherein a composition of the second layer is characterized by formula FX3 or FX4:
Ni.sub.xSb.sub.ySn.sub.1-x-yO.sub.2  (FX3); or
Ce.sub.xSb.sub.ySn.sub.1-x-yO.sub.2  (FX4); wherein x is greater than or equal to 0.01 and less than or equal to 0.05; and y is selected from the range of 0.05 to 0.1.

5. The electrode of claim 1, wherein support membrane comprises a titanium foam, a titanium mesh, titanium fibers, or a combination of these.

6. The electrode of claim 1, wherein at least 100% of a surface area of the support membrane is coated with the electrocatalytic coating.

7. The electrode of claim 1, wherein the REM has a porosity and permeability characterized by exclusion of helminth eggs and particles having a characteristic particle diameter greater than 50 μm.

8. The electrode of claim 1, wherein the REM comprises pores or channels having a characteristic pore diameter selected from the range of 50 μm to 100 μm.

9. The electrode of claim 1, wherein the electrocatalytic coating is characterized by a thickness selected from the range of 1 μm to 3 μm.

10. The electrode of claim 1, wherein the electrocatalytic coating is characterized by a charge transfer resistance of 12 Ohm or less.

11. The electrode of claim 1, wherein a cell voltage of an electrochemical cell having said electrode remains within 20% of 7V under an anodic potential of 4.5 V.sub.RHE during 2000 hours of operation.

12. The electrode of claim 1, wherein the electrode is capable of at least 2000 hours of operation an electrochemical cell under an anodic potential selected from the range of 2.7 to 5 V.sub.RHE.

13. The electrode of claim 1, wherein the electrode is an anode capable of catalyzing oxidation reactions that produce hydroxyl radicals, chlorine, reactive chlorine species, reactive oxygen species, and ozone.

14. The electrode of claim 1, wherein the REM is capable of: oxidizing perfluorinated alkyl substances, oxidizing polyfluorinated alkyl substances, inactivating E. coli., inactivating MS2 biophage, decomposing trimethoprim, decomposing ciprofloxacin, decomposing metoprolol, decomposing propranolol, decomposing carbamazepine, removing ammonium ions, and removing chemical oxygen demand (COD).

15. The electrode of claim 1, wherein the electrocatalyst coating is compatible with an aqueous solution having any pH selected from the range of 1 to 14.

16. The electrode of claim 1, wherein the REM comprises an internal face and an external face such that a liquid flows into the external face or the internal face and out through the internal face or the external face, respectively.

17. The electrode of claim 1 comprising an inlet/outlet channel for fluid flow therethrough.

18. A porous and water-permeable electrode for electrocatalysis comprising: a porous and water-permeable reactive electrochemical membrane (“REM”) comprising: a porous and water-permeable support membrane; wherein the support membrane is formed of a titanium metal; and an electrocatalytic coating on at least a portion of the metal support membrane, the electrocatalytic coating being a Ir—Ru—Ti—O layer having a composition characterized by formula FX1A:
Ir.sub.xRu.sub.yTi.sub.zO.sub.2  (FX1A); wherein: x is selected from the range of 0 to 0.1; y is selected from the range of 0.1 to 0.5; z is selected from the range of 0.5 to 0.8.

19. An electrochemical system comprising: a cathode; an anode comprising a reactive electrochemical membrane (“REM”), wherein the REM comprises: a porous and water-permeable support membrane; wherein the support membrane is formed of a titanium metal; and an electrocatalytic coating on at least a portion of the metal support membrane, the electrocatalytic coating being a tin oxide bilayer comprising: a first layer adjacent to and directly contacting the metal support membrane; wherein the first layer comprises tin oxide doped with antimony; and a second layer adjacent to and directly contacting the first layer; wherein the second layer forms a surface of the REM such that the second layer is in direct contact with an aqueous solution when the REM is in contact with the aqueous solution; wherein the second layer comprises tin oxide doped with antimony and nickel or cerium; wherein the REM is porous and water-permeable; and the aqueous solution having at least one contaminant wherein a composition of the first layer is characterized by formula FX2:
Sb.sub.xSn.sub.1-xO.sub.2  (FX2); wherein x is greater than or equal to 0.1 and less than or equal to 0.5.

20. The system of claim 19, wherein the aqueous solution is a greywater.

21. An electrochemical system comprising: a cathode; an anode comprising a reactive electrochemical membrane (“REM”), wherein the REM comprises: a porous and water-permeable support membrane; wherein the support membrane is formed of a titanium metal; and an electrocatalytic coating on at least a portion of the metal support membrane, the electrocatalytic coating being a Ir—Ru—Ti—O layer having a composition characterized by formula FX1:
Ir.sub.xRu.sub.yTi.sub.zO.sub.2  (FX1); wherein: x is selected from the range of 0 to 0.1; y is selected from the range of 0.1 to 0.5; z is selected from the range of 0.5 to 0.8 an aqueous solution having at least one contaminant.

22. A method of decontaminating an aqueous solution, the method comprising step of: (a) contacting an anode and a cathode with the aqueous solution having at least one contaminant; wherein the anode comprises: a porous and water-permeable reactive electrochemical membrane (“REM”) comprising: a porous and water-permeable support membrane; wherein the support membrane is formed of a titanium metal; and an electrocatalytic coating on at least a portion of the metal support membrane, the electrocatalytic coating being a tin oxide bilayer comprising: a first layer adjacent to and directly contacting the metal support membrane; wherein the first layer comprises tin oxide doped with antimony; and a second layer adjacent to and directly contacting the first layer; wherein the second layer forms a surface of the REM such that the second layer is in direct contact with an aqueous solution when the REM is in contact with the aqueous solution; wherein the second layer comprises tin oxide doped with antimony and nickel or cerium; wherein a composition of the first layer is characterized by formula FX2:
Sb.sub.xSn.sub.1-xO.sub.2  (FX2); wherein x is greater than or equal to 0.1 and less than or equal to 0.5; and (b) applying to the anode an anodic potential; and (c) decomposing the at least one contaminant.

23. A method of making a reactive electrochemical membrane (REM), the method comprising: first immersing a porous and water-permeable support membrane into a first precursor solution; wherein: the support membrane is formed of a titanium metal; the first precursor solution comprises a tin compound, an antimony compound, and a flammable alcohol; first calcinating the support membrane to form a first layer having a composition comprising antimony-doped tin oxide; second immersing the support membrane into a second precursor solution, wherein: the second precursor solution comprises a tin compound, an antimony compound, a flammable alcohol, and a nickel compound or a cerium compound; and second calcinating the support membrane to form a second layer on the first layer, the second layer having a composition comprising antimony- and nickel-doped tin oxide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1. Challenges in plate-type electrode configurations.

(2) FIGS. 2A-2B. Advantages of Reactive Electrochemical Membrane. FIG. 2A.

(3) Schematic of a conventional electrochemical reaction (ECR) system. FIG. 2B. Scematic of a system using a REM.

(4) FIG. 3. Photograph of exemplary support membranes for REM.

(5) FIG. 4. Series of photographs corresponding to a method of forming an REM, with electrocatalytic coating, according to certain embodiments. A Ni—Sb—SnO.sub.2 coating is loaded onto Ti filter by dip-coating.

(6) FIGS. 5A-5B. Reacative Electrochemical Membrane. FIG. 5A. L3 commercial Ti metal filter $6 and Ni—Sb—SnO2 loaded REM. FIG. 5B. Electrochemical Surface Area ECSA (cm.sup.2)=4.9 mF/0.04 mF.Math.cm.sup.−2=122 cm.sup.2.

(7) FIGS. 6A-6B. Elemental analysis of support membrane formed of titanium (FIG. 6A) and elemental analysis of NAT/ATO coating on REM, showing an atomic ratio of Sn/Sb/Ni being 1/0.05/0.008.

(8) FIG. 7. Stability of REM; REM coupled with SS cathode; 50 mM Na.sub.2SO.sub.4; 1 A.

(9) FIGS. 8A-8C. Perfluoroalkyl substances (PFAS) oxidation process illustration.

(10) FIG. 8A. The involvement of DET is supported by PFAS oxidation. FIG. 8B. Illustration of an electrochemical system, according to certain embodiments disclosed herein, for decomposition of contaminants, such as PFAS. FIG. 8C. Relative concentration of PFOS and PFOA contaminants over time during decontamination using an electrochemical system, according to certain embodiments disclosed herein.

(11) FIGS. 9A-9B. Toilet Wastewater Treatment. FIG. 9A. 300 mL toilet wastewater collected from Caltech Solar toilet; 1 A current. FIG. 9B. Energy Consumption (Wh/L) ECR: >60 VS REM: 34.

(12) FIG. 10. Combine REM with Anaerobic Digestion. Energy Consumption (Wh/L) A/A/O+ECR: 29 VS ST+REM: 8.5.

(13) FIG. 11. Photographs and schematic showing combination of REM with Ion Exchange Membrane.

(14) FIG. 12. Photographs and schematic showing combination of REM with membrane electrolysis for aged urine treatment.

(15) FIGS. 13A-13B. New Electrode Performance. FIG. 13A. Activity of IrRuTi anode in toilet wastewater. FIG. 13B. Experimental data demonstrating chlorine evolution rate over time during operation of an electrochemical system having a Ti/Ir electrode, as illustrated in FIG. 13A (left), squares, versus an electrochemical system, according to certain embodiments disclosed herein, having an IRTO layer (circles). Both electrodes in a plate or flow-by configuration in this example.

(16) FIGS. 14A-14B. New electrode allows for reduction of energy consumption without compromising the wastewater treatment efficiency. FIG. 14A. OpeEX and CapEX reduction of Electrochemical Chemical Reactor (ECR) units. FIG. 14B. Photograph of a conventional electrochemical system (left) compared to an electrochemical system (right), according to certain embodiments disclosed herein.

(17) FIG. 15. Adopting IrRuTiOx electrode in the electrochemical reactor can reduce 70% of the overall cost. OpeEX and CapEX reduction of ECR units.

(18) FIG. 16. Photo of titanium filter (left) and REM electrode (right).

(19) FIG. 17. Schematic demonstration of the REM based electrochemical water treatment process and the pore structure of the NATO/ATO REM after the loading of catalysts.

(20) FIG. 18A. SEM image of the cross-section of the NAT/AT coated on titanium plate. Point EDS elementary analysis of (FIG. 18B) Ni and (FIG. 18C) Sn/Sb ratio based on the weight percentage.

(21) FIG. 19. A data plot corresponding to electrochemical impedance spectroscopy (EIS) for AT, NAT/AT, and NAT REMs. By modeling the electrochemical cell using a Randles equivalent circuit, the charge transfer resistance (R.sub.ct) for AT, NAT/AT, and NAT REM's are determined to be 4 Ohm, 12 Ohm, and 125 Ohm, respectively.

(22) FIGS. 20A-20B. Electrochemical production of (FIG. 20A) chlorine (in 30 mM NaCl) and (FIG. 20B) ozone (in 15 mM Na.sub.2SO.sub.4) by REM with AT or NAT/AT coatings. Electrolyte volume: 150 mL; Current: 1 A; Geometric area of REM: 45 cm.sup.2.

(23) FIG. 21. Electrochemical degradation of benzoic acid (BA, 1 mM) as a probe molecule reactive toward hydroxyl radicals.

(24) FIG. 22. Electrochemical treatment of latrine wastewater using NAT/AT REM electrode. Wastewater volume: 300 mL; Current: 1 A; Geometric area of REM: 45 cm.sup.2.

(25) FIG. 23. Removal of five typical pharmaceuticals and personal care products (10 μM each) in the latrine wastewater by NAT/AT REM. Wastewater volume: 150 mL; Current: 1 A; Geometric area of REM: 45 cm.sup.2.

(26) FIG. 24A-24B. Inactivation of (FIG. 24A) E. coli. and (FIG. 24B) MS2 in 30 mM NaCl or 15 mM Na.sub.2SO.sub.4. Electrolyte volume: 150 mL; Current: 1 A; Geometric area of REM: 45 cm.sup.2.

(27) FIG. 25A. Configuration of REM reactor for PFAS treatment. (FIG. 25B and FIG. 25C) removal of PFAS in real landfill leachate by EOF.

(28) FIG. 26. Stability test of the NAT/AT REM. Electrolyte volume: 150 mL; Current: 1 A; Current density: 10 mA/cm.sup.2; Geometric area of REM: 45 cm.sup.2.

(29) FIG. 27. EIS analysis. EIS conducted in a mixture of K.sub.3Fe(CN).sub.6, K.sub.4Fe(CN).sub.6, and KCl; NAT/ATs have a lot smaller charge transfer resistance (RCT) comparing to NAT.

(30) FIG. 28. Chlorine evolution and ozone production. Addition of Ni leads to lower CER activities and 03 production; when chloride (Cl.sup.−) present, 03 produced with a slower rate; O.sub.3 consumed when benzoic acid (BA) present.

(31) FIGS. 29A-29B. Data showing decomposition of benzoic acid (BA) via hydroxyl radical generation using REM under a variety of conditions. Left panel shows effect of different electrocatalytic coating compositions. The NAT/AT coating has highest HO.Math.production rate compared to only the NAT or only the AT layer. Middle and right panels correspond to use of REM with NAT/AT coating with different aqueous solution (or, electrolyte) compositions. A presence of t-BuOH or t-BuOH/MeOH inhibits HO.Math.mediated reaction. The remaining BA removal may result from direct electron transfer (DET). When chloride (Cl.sup.−) is present, slower BA degradation is observed.

(32) FIG. 30. Data and considerations pertaining to ozone production in NaCl.

(33) FIG. 31. Data and considerations pertaining to benzoic acid (BA) degradation using REM with NAT/AT.

(34) FIG. 32. Data and considerations pertaining to benzoic acid (BA) degradation in NaCl.

(35) FIG. 33. Trace organic degradation. Rapid removal of pharmaceutical compounds from pure electrolytes; fast removal of CBZ recorded in both NaClO.sub.4 and NaCl electrolytes with similar rates.

(36) FIG. 34. Pathogen inactivation. E. coli. and MS2 were spiked to Na.sub.2SO.sub.4 and NaCl electrolytes. Fast disinfection in both cases; disinfection mechanism not based on chlorine-mediated oxidation.

(37) FIG. 35. COD and spiked PPCP removal from wastewater. Collected from Caltech toilet and one-week anaerobic pretreatment; fast COD removal 100 mg/L within 75 min.); significant removal of all spiked pharmaceutical compounds.

(38) FIG. 36. Schematic of system employing an electrode with a reactive electrochemical membrane (REM). Benefits include enhanced mass transfer and size exclusion.

(39) FIG. 37. Relative concentration of benzoic acid (BA) vs time at different current densities using REM with NAT/AT, according to certain embodiments.

(40) FIG. 38. Photographs of REM and reactor prototypes.

(41) FIG. 39. Heterogeneous catalytic ozonation (HC). Nonradical oxidation processes in the HCO of organics; mechanism of ozone activation on the surface HO groups.

(42) FIG. 40. XPS data for (left) AT-only coating and (right) NAT/AT coating.

(43) FIG. 41. Relative concentration vs time showing BA degradation in different pH.

(44) FIG. 42. Coating—Ni—Sb—SnO.sub.2. O.sub.3 as an environmentally-friendly oxidant; high redox potential; cleaner transformation byproducts; facilitates OH radical formation.

(45) FIG. 43. Ozone production. Production of ozone as a unique advantage of NATO coating; electrolyte rapidly saturated with ozone (blue dots) within ˜15 min.

(46) FIG. 44. Photograph of several types of electrodes having REM with different electrocatalytic coatings. “BNTA” refers to the bilayer tin oxide having NAT as second layer and AT as first layer. The dip-coating method for depositing a electrocatalytic coating on the membrane is proved to be versatile for any type of surface and pore structure.

(47) FIG. 45. Photograph showing in-situ cleaning by back washing.

(48) FIG. 46. (Left) data corresponding to hydroxyl radical generation using NATO coating on a plate-type electrode and (right) data corresponding to hydroxyl radical generation using an REM with NAT/AT coating. Benzoic acid (BA) removal is an indicator for hydroxyl radical generation. The left panel suggests the presence of chloride inhibited the removal of BA, which indicates the removal of organics by NATO does not require addition of Cl.sup.− and that excessive amount of Cl.sup.− might lead to an adverse effect.

(49) FIG. 47. Disinfection data using REM with NAT/AT. E. coli. and MS2 spiked to Na.sub.2So.sub.4 and NaCl electrolytes; more than 4-log removal of E. coli. and MS2 achieved with 30 s; efficient disinfection could still be achieved in the absence of Cl.sup.−.

(50) FIG. 48. Toilet wastewater treatment data using REM with NAT/AT. COD. Chemical oxygen demand (COD) removal in wastewater; 250 mL toilet wastewater collected from Caltech Solar toilet treated with 1 A current.

(51) FIG. 49. Toilet wastewater treatment data using REM with NAT/AT. Degradation of trace organic contaminants in wastewater; simultaneous removal of a selection of pharmaceutical and personal care products (PPCPs) within 1 h in toilet wastewater.

(52) FIG. 50. Greywater treatment data using REM with NAT/AT. COD removal in greywater, total nitrogen (TN) negligible; Run1: 250 mL greywater made with NSF recipe treated with 1 A current; Run2: 250 mL hand-washing greywater using VWR antimicrobial hand soap (large amount) treated with 1 A current.

STATEMENTS REGARDING CHEMICAL COMPOUNDS AND NOMENCLATURE

(53) In general, the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the invention.

(54) The term “water-permeable” refers to a membrane, electrode, film, layer, coating, or any other material or item that is permeable to water or through which liquid water may penetrate and flow.

(55) The term “porous” refers to a membrane, electrode, film, layer, coating, or any other material or item that has porosity. The term “porosity” refers to the amount of a material or item, such of a membrane, corresponding to an absence of said material or item, such as absence corresponding to pores, such as apertures, channels, voids, etc. Generally, porosity refers to absence of said material or item within the physical bounds of said material or item, such as due to the material or item having a porous internal structure. Porosity may be expressed as the percentage of the volume of a material or item, which corresponds to pores, such as apertures, channels, voids, etc., relative to the total volume occupied by the material or item.

(56) Porosity can also be characterized by characterizing the pores of the porous material or item. For example, pores can be characterized by a “size characteristic.” For example, a size characteristic of pores is a “characteristic pore diameter,” which may be an empirically-derived value. A characteristic pore diameter refers to an average cross-sectional diameter or cross-sectional width of the pores of a porous material or item.

(57) The term “size characteristic” refers to a property, or set of properties, of a pore or particle that directly or indirectly relates to a size attribute of the pore or particle. According to some embodiments, a size characteristic corresponds to an empirically-derived size characteristic of a pore or particle(s) being detected, such as a size characteristic based on, determined by, or corresponding to data from any technique or instrument that may be used to determine a pore size or particle size, such as electron microscopy (e.g., for characterizing particles or pores; e.g., SEM and TEM), mercury intrusion porosimetry (e.g., for characterizing pores), a bubble gas transport technique (e.g., for characterizing pores), adsorption-desorption technique such as a Barett-Joyner-Halenda method (e.g., for characterizing pores), a permporometry technique (e.g., for characterizing pores), a thermoporometry technique (e.g., for characterizing pores), a gas permeability technique (e.g., for characterizing pores), optical microscopy (e.g., for characterizing pores or particles), mass transport technique (e.g., for characterizing pores), or a light scattering technique (e.g., for characterizing particle; e.g., DLS). For example, in reference to a particle, a size characteristic can correspond to a spherical particle exhibiting similar or substantially same properties, such as aerodynamic, hydrodynamic, optical, and/or electrical properties, as the particle(s) being detected). According to some embodiments, a size characteristic corresponds to a physical dimension, such as length, width, thickness, or diameter. Size characteristics of a pore include length, width, diameter, surface area, geometrical parameter, or void volume in the pore. A plurality of pores can be characterized by an average size characteristic, such as an empirically-derived numerical average of the respective size characteristic of each pore of the plurality of pores. A pore may be a longitudinal pore, for example. A longitudinal pore is one whose length is at least 20% greater than its diameter (or, than width of its void volume, for example, if diameter is not an appropriate characteristic).

(58) The term “support membrane” refers to a base or substrate item that is a support or substrate of a reactive electrochemical membrane and capable of supporting or being a substrate for an eletrocatalytic coating.

(59) The term “electrochemical system” refers to devices and/or device components, such as one or more electrochemical cells, that perform electrochemistry. Electrochemistry refers to conversion of chemical energy into electrical energy or electrical energy into chemical energy. Chemical energy can correspond to a chemical change or chemical reaction. Electrochemistry can thus refer to a chemical change (e.g., a chemical reaction of one or more chemical species into one or more other species) generating electrical energy and/or electrical energy being converted into or used to induce a chemical change. Examples of a chemical change or chemical reaction include oxidation of a contaminant or pollutant and/or formation of an oxidant or other reactive species that can oxidize a contaminant or pollutant. Electrical energy refers to electric potential energy, corresponding to a combination of electric current and electric potential in an electrical circuit. An exemplary electrochemical system or electrochemical cell is an electrolytic cell. Electrochemical cells have two or more electrodes (e.g., negative and positive electrodes; e.g., cathode and anode) and one or more electrolytes. An anode is defined as the electrode at which oxidation occurs, or, in other words, a chemical change being an oxidation occurs at the anode. A cathode is defined as the electrode at which reduction occurs, or, in other words, a chemical change being a reduction occurs at the cathode. An electrolyte may include species that are oxidized and species that are reduced during charging or discharging of the electrochemical cell. An exemplary electrolyte is be wastewater or an aqueous solution, such as an aqueous solution comprising one or more contaminants. For example, the electrolyte is an aqueous solution. Reactions occurring at the electrode, such as sorption and desorption of a chemical species or such as an oxidation or reduction reaction, contribute to charge transfer processes in the electrochemical cell. Electrochemical oxidation may occur at the cathode, for example, and electrochemical reduction may occur at the anode, for example. Electrochemical oxidation refers to a chemical oxidation reaction accompanied by a transfer of electrical energy (e.g., electrical energy input driving the oxidation reaction) occurring in the context an electrochemical cell. Similarly, electrochemical reduction refers to a chemical reduction reaction accompanied by a transfer of electrical energy occurring in the context an electrochemical cell. The term “electrochemically” or “electrochemical” may describe a reaction, process, or a step thereof, as part of which chemical energy is converted into electrical energy or electrical energy is converted into chemical energy. For example, a product may be electrochemically formed when electrical energy is provided to help the chemical conversion of a reactant(s) to the product proceed. The term “non-electrochemical” refers to a reaction or process that does not include electrochemistry and/or does not require electrochemistry in order to be performed.

(60) The term “electrocatalyst” refers to a catalyst that participates in or facilitates an electrochemical process or reaction. The term “electrocatalytic” refers to a material or item that is or is capable of being an electrocatalyst. For example, an electrocatalytic coating is a coating that is or is capable of being an electrocatalyst.

(61) Electrochemical water treatment refers to water treatment, water decontamination, or water purification that is aided, facilitated, or performed via electrochemistry using an electrochemical system. As used herein, the terms “water decontamination,” “water treatment,” and “water purification” can be used interchangeably and are generally intended to refer to removal of one or more pollutants or contaminants. In electrochemical water decontamination, the removal of one or more contaminants is aided, facilitated, or performed by electrochemistry, such as via electrochemical decomposition or destruction of the one or more contaminants. Electrochemical water decontamination may include non-electrochemical processes for removing contaminants from water, such as physical processes, such as filtration. For example, a reactive electrochemical membrane combines physical exclusion/filtration and electrochemical processes, such as electrochemical oxidation, to remove and decompose/destroy contaminants. Electrochemical decomposition or destruction of a contaminant can be direct or indirect. For example, direct electrochemical decomposition of a contaminant refers to electrochemical decomposition or destruction of the contaminant at an electrode, such as at the anode, such as at an REM or electrolytic coating thereof, in response to electrical energy at the electrode, such as electrooxidation of the contaminant at the anode in response to an anodic potential, optionally catalyzed by an electrocatalytic coating. For example, indirect electrochemical decomposition of a contaminant refers to decomposition or destruction of the contaminant by oxidant or other reactive species that are formed electrochemically at an electrode of an electrochemical system. Generally, decomposition or destruction of a contaminant refers to change of physical characteristics (e.g., characteristic particle size, etc.) and/or chemical characteristics (e.g., composition, formula, structure, etc.) of the contaminant, preferably such that the contaminant is no longer a contaminant.

(62) The terms “contaminant” and “pollutant” are used interchangeably and refer to a species in a solution, preferably an aqueous solution, that is undesired and intended to be removed, or at least have its concentration reduced, using water decontamination. Optionally, contaminants are species that are toxic to humans or animals. Optionally, contaminants are species whose presence in a solution is prohibited or otherwise discouraged according to health and safety, or any other, regulations and/or whose concentration is greater than permitted or than recommended according to health and safety, or any other, regulatory rules or laws in effect where the solution is generated, used, processed, distributed, and/or sold. For example, water intended for human consumption is subject to various regulations wherein materials prohibited from being in such water or materials present at a concentration at or above a prohibited threshold for such water are considered contaminants. Contaminants can be particulates, molecules, compounds, salts, ions, atoms, toxins, other chemical agents, biological agents, such as bacteria, viruses and fungi, and any other such chemical and/or physical species. For example, contaminants in a solution can be dissolved, dispersed, and/or suspended in the solution. Contaminants can be characterized as contaminants by their physical characteristics (e.g., characteristic particle size) and/or chemical characteristics (e.g., composition, formula, structure). Generally, the term “wastewater” refers to water or aqueous solution that comprises one or more contaminants or pollutants. Optionally, wastewater refers to water or aqueous solution that is a waste product of a process, such as an industrial process, which has one or more contaminants or pollutants. Greywater, such as wastewater generated in households and/or office building from streams without fecal contamination, and blackwater, such as wastewater comprising sewage or fecal contamination, are examples of wastewater or water having one or more contaminants or pollutants. Decontamination or purification of greywater is contemplated herein using electrodes, systems, and methods disclosed herein. Decontamination or purification of blackwater is contemplated herein using electrodes, systems, and methods disclosed herein.

(63) Generally, as used herein, the terms “oxidants” and “reactive species” refer to chemical species that can chemically decompose or destroy, such as by chemical oxidation, one or more contaminants or pollutants. As such, generally, oxidants and reactive species, as referred to herein, can facilitate indirect electrochemical decomposition or destruction of one or more contaminants. Such oxidants and reactive species include, but are not limited to, any one or combination of hydroxyl radicals, chlorine, reactive chlorine species, reactive oxygen species, and ozone.

(64) “Fluid communication” refers to the arrangement of two or more materials or items such that a fluid can be transported to, past, through, and/or from one material or item to another. For example, in some embodiments two materials or items are in fluid communication with one another if a fluid flow path is provided directly between the two materials or items. In some embodiments, two materials or items are in fluid communication with one another if a fluid flow path is provided indirectly between the two materials or items, such as by including one or more other materials or items or flow paths between the two materials or items. In one embodiment, two materials or items present in a body of fluid are not necessarily in fluid communication with one another unless fluid from the first material or item is drawn to, past and/or through the second material or item, such as along a flow path.

(65) “Ionic communication” refers to the arrangement of two or more materials or items such that ions can be transported to, past, through, and/or from one material or item to another. Generally, ions can pass through ionically conducting materials such as ionically conducting liquids, such as water, or through solid ionic conductors. Preferably, but not necessarily exclusively, as used herein, transport or conduction of ions refers to transport or conduction of ions in an aqueous solution. For example, in some embodiments two materials or items are in ionic communication with one another if a path of ion flow is provided directly between the two materials or items. In some embodiments, two materials or items are in ionic communication with one another if an ion flow path is provided indirectly between the two materials or items, such as by including one or more other materials or items or ion flow paths between the two materials or items. In one embodiment, two materials or items are not necessarily in ionic communication with one another unless ions from the first material or item are drawn to, past and/or through the second material or item, such as along an ion flow path.

(66) The term “electrical communication” refers to the arrangement of two or more materials or items such that electrons can be transported to, past, through, and/or from one material or item to another. Electrical communication between two materials or items can be direct or indirect through another one or more materials or items. Generally, materials or items in electrical communication are electrically conducting or semiconducting.

(67) In some embodiments, the term “aqueous” refers to a solution where the solvent is water such that other species of the solution, or solutes, are substantially solvated by water. In some embodiments, the term “aqueous” may generally refer to a solution comprising water. Optionally, but not necessarily, an aqueous solution or an aqueous solvent includes 20 vol. % or less, optionally 15 vol. % or less, optionally 10 vol. % or less, optionally 5 vol. % or less, of non-aqueous solvent and/or solute species.

(68) The term “pump” generally refers to an instrument that can induce flow of a liquid, include any instrument conventionally referred to as a pump. The term “pumping” refers to inducing of flow of a liquid, such as using a pump.

(69) The term “at. %” refers to atomic percent. For example, 0.3 at. % of antimony in the first layer (the AT or ATO layer) refers to 0.3% being a ratio, represented as a percent, of an amount of the element Sb to the sum of the amount of all other elements in the first layer, which are typically Sb, Sn, and O. For example, 0.3 at. % of the element antimony in the second layer (the NAT or NATO layer) refers to 0.3% being a ratio, represented as a percent, of an amount of the element Sb to the sum of the amount of all other elements in the second layer, which are typically Ni, Sb, Sn, and O or Ce, Sb, Sn, and O.

(70) Generally, the term “doped” has an art-recognized meaning and refers to a host material, such as tin oxide, comprising other elements (dopants), such as antimony, nickel, and/or cerium, generally as a result of said other elements being intentionally introduced to the host material, during formation of the host material and/or after the host material is formed. As used herein, the term doped or doping is not exclusive of the art-known terms alloyed or alloying, respectively. Generally, description of a host material doped with a dopant material or element may be understood to refer to the host material comprising the dopant material or element.

(71) In an embodiment, a composition or compound of the invention, such as an alloy or precursor to an alloy, is isolated or substantially purified. In an embodiment, an isolated or purified compound is at least partially isolated or substantially purified as would be understood in the art. In an embodiment, a substantially purified composition, compound or formulation of the invention has a chemical purity of 95%, optionally for some applications 99%, optionally for some applications 99.9%, optionally for some applications 99.99%, and optionally for some applications 99.999% pure.

DETAILED DESCRIPTION OF THE INVENTION

(72) In the following description, numerous specific details of the devices, device components and methods of the present invention are set forth in order to provide a thorough explanation of the precise nature of the invention. It will be apparent, however, to those of skill in the art that the invention can be practiced without these specific details.

(73) The invention can be further understood by the following non-limiting examples.

Example 1: Reactive Electrochemical Membrane (REM) for Wastewater Treatment

(74) Compared with the plate-type electrode configuration for wastewater treatment, the reactive electrochemical membrane (REM) described here is more efficient in terms of organic oxidation (i.e. COD reduction). As shown in FIGS. 9A-9B, the conventional electrochemical reactor (ECR) equipped with plate type electrode requires 60 Wh/L to treat the toilet water to meet reuse standard, while that of REM is 34 Wh/L.

(75) As shown in FIGS. 10-12, REM can be integrated with other treatment technique such as anaerobic digestion and membrane electrolysis to further enhance its performance.

(76) Challenges in plate-type electrode configurations include stability of anode material and mass transfer limitation. Advantages of Reactive Electrochemical Membrane include enhanced mass transfer and size exclusion.

(77) In reference to FIG. 3, a sintered titanium filter can be used as a support membrane for an REM according to embodiments disclosed herein. In reference to FIG. 4, a Ni—Sb—SnO2 coating can be loaded onto Ti filter by dip-coating. In reference to FIG. 5A, an L3 commercial Ti metal filter (left) can be loaded with a Ni—Sb—SnO2 electrocatalytic coating (right) to make an REM. In reference to FIG. 5B, the electrochemical surface area (ECSA (cm.sup.2)) is determined to be 4.9 mF/0.04 mF.Math.cm.sup.−2=122 cm.sup.2, for example. In reference to FIG. 6B, an atomic ratio of Sn/Sb/Ni is 1/0.05/0.008. FIG. 7 shows cell voltage stability of REM in an electrochemical cell (REM coupled with SS cathode; 50 mM Na.sub.2SO.sub.4; 1 A). FIGS. 8A-8C show perfluoroalkyl substances (PFAS) oxidation. The involvement of DET is supported by PFAS oxidation.

(78) FIG. 9A shows toilet Wastewater (left) treated (right) using an electrode, according to certain embodiments disclosed herein, having an NAT/AT coating (300 mL toilet wastewater collected from Caltech Solar toilet; 1 A current. Using an electrode as disclosed herein corresponds to lower energy Consumption (Wh/L) vs. ECR: ECR: >60 VS REM: 34.

(79) In reference to FIG. 10, the electrodes and systems disclosed herein can be combined with anaerobic digestion. Energy consumption (Wh/L) can be reduced this way compared to conventional approaches of A/A/O+ECR: 29 vs. ST+REM: 8.5.

(80) In reference to FIG. 11, the electrodes and systems disclosed herein can be combined with an ion exchange membrane. In reference to FIG. 12 the electrodes and systems disclosed herein can be combined membrane electrolysis, such as for aged urine treatment.

Example 2: IrRuTiOx Electrode for Wastewater Treatment

(81) Background of Electrode Technology Used in Wastewater Treatment

(82) The previously developed TiO.sub.2/IrTaO.sub.x electrode shows high chlorine generation activity initially, but it will be gradually deactivated in wastewater electrolysis, evidenced by the 80% reduction of chlorine generation rate after 100 h electrolysis. Besides, the manufacture of TiO.sub.2/IrTaO.sub.x requires multiple times of coating, which increases the cost.

(83) New Electrode Recipe

(84) We developed a IrRuTiO.sub.x electrode recipe. It is prepared by dip- or brush-coating Ti plate with citrate complexed metal precursors in ethylene glycol, followed by thermal annealing in 450° C. The optimum loading of IrRuTiO.sub.x is determined as 0.5 mg/cm.sup.2. Details of making metal precursors are shown below.

(85) 1) Add 12.6 g citric acid monohydrate to 16 mL Ethylene glycol; heat at 90° C. till complete dissolution.

(86) 2) Add 0.48 g Titanium oxysulfate anhydrous, 0.15 g RuCl.sub.3 and 0.03 g IrCl.sub.3 to the above solution, stir till complete dissolution

(87) 3) Cool down to room temperature and adjust the volume to 50 mL by ethylene glycol.

(88) Advantages of Electrode Made with New Recipe

(89) FIGS. 13A-13B show that the IrRuTiO.sub.x electrode exhibits significantly better stability in wastewater compared with TiO.sub.2/IrTaO.sub.x electrode. The former one can maintain 50% of chlorine evolution activity while the latter loses 80% of activity after 100 h electrolysis in wastewater. FIGS. 13A-13B show experimental data demonstrating chlorine evolution rate over time during operation of an electrochemical system having a Ti/Ir electrode, as illustrated in FIG. 13A (left), squares, versus an electrochemical system, according to certain embodiments disclosed herein, having an IRTO layer (circles). Both electrodes in a plate or flow-by configuration in this example. Activity of IrRuTi anode in toilet wastewater. (Continuously operated in raw toilet wastewater at 10 mA/cm.sup.2. Electrodes were taken out periodically to analyze chlorine evolution rate in 30 mM naCl.)

(90) This high performance of IrRuTiO.sub.x enable the miniaturization of reactor and the reduction of energy consumption without compromising the wastewater treatment efficiency (FIGS. 14A-14B).

(91) There is also a significantly reduction of electrode manufacture cost thanks to the simple one-layer structure of IrRuTiO.sub.x electrode.

(92) As shown in FIG. 15, adopting IrRuTiO.sub.x electrode in the electrochemical reactor could reduce 70% of the overall cost. Adopting IrRuTiO.sub.x electrode in the electrochemical reactor can reduce 70% of the overall cost.

(93) OpeEX and CapEX reduction of Electrochemical Chemical Reactor (ECR) units

(94) Electrode Reactor Reaction ECR Bio-Total Energy Electrode

(95) TABLE-US-00001 Electrode Reactor Reaction ECR Bio- Total Energy Electrode Array Q'ty volume Time energy Pretreatment Consumption* Ti/Ir 4 105 L 60 min 22.79 Wh/L  6.2 Wh/L 28.99 Wh/L IrRuTi 1  28 L 10 min  5.72 Wh/L 5.48 Wh/L  11.2 Wh/L *Effluent [COD] and [NH4.sup.+] meets ISO 30500 category A usage.

Example 3: REM Synthesis

(96) Citric acid (12.6 g) was added to ethylene glycol (20 mL) and heated to 90° C. till the citric acid is completely dissolved. Metal salts were then added to the solution to form metal-organic complexes. The clean solution is then diluted by ethanol to 50 mL. Precursor for Sb—SnO.sub.2 layer contained 360 mM SnCl.sub.2 (98%, Aldrich) and 40 mM SbCl.sub.3 (>99.0%, Aldrich), while precursor for Ni—Sb—SnO.sub.2 layer contained 360 mM SnCl.sub.2, 15 mM SbCl.sub.3, and 4 mM Ni(OCOCH.sub.3) (98%, Aldrich).

(97) For the preparation of reactive electrochemical membrane (REM) electrodes, the titanium porous filter cartridge (FIG. 16), discs, or any form of porous titanium metal substrate is immersed into the Sb—SnO.sub.2 precursor solution. After the micropores of the Ti filter are saturated with the precursor solution, the Ti filter is pulled out of the solution and hang vertically to drain the excessive solution on the external surface. The coated filter is then transferred to an oven at 600° C. Flame will be ignited on the filter to initiate the combustion synthesis of metal oxide layers within the pore structure. The dip-coating and following calcination processes can be repeated several times to reach the desired catalyst loading.

(98) The antimony doped tin oxide (AT: Sb—SnO.sub.2) REM electrode can be prepared by coating the Ti filter backbone with Sb—SnO.sub.2. The nickel and antimony co-doped tin oxide (NAT) can be further coated on the ATO REM to form NAT/AT REM with enhanced performance (vide infra).

(99) The Ni(OCOCO.sub.3) in the precursor solution can be replaced by 4 mM Ce(NO.sub.3).sub.3. Ce—Sb—SnO.sub.2 coating has the same performance as Ni—Sb—SnO2 on chlorine generation, ozone production, and radical production. The addition of ethanol is a critical step of this invention. Ethanol reduces the surface tension of precursor, enabling the precursor solutions to fully penetrate into the micro-porous structure of the Ti filter. Ethanol also serves as a fuel to initiate the flame-combustion synthesis reaction.

Example 4: Methods for Water Treatment

(100) Any tank that can hold water and accommodate the REM electrodes can serve as the reactor. The REM reactor is filled with wastewater. A REM anode is immersed in the water, and a Ti mesh cathode is placed peripherally around the anode. Wastewater was pumped out from the filter anode (FIG. 17). The effluent can be discharged or recycled back to the tank. During the filtration, anodic potential can be applied to the REM electrode to catalyze the electrochemical oxidation reaction. Electrocatalysts embedded within the pore channels (50-100 μm) produce oxidants, including hydroxyl radicals, chlorine, and ozone, to react with pollutants during water filtration. Large particles such as suspended solids and helminth eggs can be filtered via the size exclusion effect.

Example 5: Electrode Characterization: Electrode Structure

(101) In order to investigate the structure of the NATO/ATO bilayer coating, a flat titanium plate was firstly coated with ATO then NATO. The cross-section of the coated plate was investigated by SEM-EDS. As shown in FIGS. 18A-18C, the top NAT layer contains ca. 0.5 wt % of Ni, while the AT layer beneath does not contain Ni. It is also found that the NAT layer has a lower amount of Sb than the AT layer, which is in line with the compositions of the corresponding precursor solutions.

Example 6: Electrode Characterization: Charge Transfer Resistance

(102) The change transfer was investigated by electrochemical impedance spectroscopy (EIS). By modeling the electrochemical cell using a Randles equivalent circuit, the charge transfer resistance (R.sub.ct) for AT, NAT/AT, and NAT REM's are 4 Ohm, 12 Ohm, and 125 Ohm, respectively. A lower R.sub.ct indicates a longer service life of the electrode. The AT coating features long service life, but the leaching of Sb.sup.3+, a toxic heavy metal ion, limits the application of AT REM in treating environmental water. Compared with the AT catalyst, the NAT catalyst shows higher performance on electrochemical water treatment due to the production of 03 as a supplement to the existing reactions of radical and chlorine production; NAT with lower Sb.sup.3+ doping level also releases a negligible amount of Sb.sup.3+ under anodic potential, but it is estimated to have a shorter service life. This invention uses NAT as the exterior catalytic layer and use AT as the inter-layer to facilitate the electron conduction.

Example 7: Electrode Characterization: Chlorine Generation

(103) FIGS. 20A-20B demonstrate the performance of AT REM and NAT/AT REM on chlorine generation. The AT REM has a higher chlorine evolution rate than the NAT/AT REM (0.16 vs. 0.1 mmol/m.sup.2/s). The NAT/AT REM can produce ozone at a rate of 0.022 mmol/m.sup.2/s, corresponding to a current efficiency of 15%, while the AT REM was not able to produce ozone.

Example 8: Electrode Characterization: Product of Hydroxyl Radicals

(104) The production of hydroxyl radicals was investigated by the degradation of benzoic acid (BA) as the probe molecule. As shown in FIG. 21, the [BA] decreases as functions of electrolysis duration. This indicates the continuous production of hydroxyl radicals to react with BA. The radical production rates, which are positively correlated with the BA degradation kinetics, can be adjusted by the current density.

Example 9: Exemplary Applications: Latrine Wastewater Treatment

(105) The NAT/AT REM was used to treat latrine wastewater collected from a decentralized sewage treatment system. FIG. 22 shows that the NAT/AT REM could effectively remove NH.sub.4.sup.+ and chemical oxygen demand (COD) in the latrine wastewater. NH.sub.4.sup.+ was removed by electrochemically generated chlorine via the breakpoint chlorination reactions. The COD removal was jointly contributed by the oxidation reactions mediated by hydroxyl radicals, chlorine, and ozone.

Example 10: Exemplary Applications: Removal of Pharmaceuticals and PPCPs

(106) The transformation of five typical pharmaceuticals and personal care products (PPCPs) was investigated (FIG. 23). PPCPs (10 μM each) spiked to the latrine wastewater were rapidly removed within 60 min.

Example 11: Exemplary Applications: Bacteria and Virus Inactivation

(107) The inactivation of model bacteria (E. coli.) and virus (MS2 biophage) by the NAT/AT REM was investigated. Five-log inactivation of E. coli. and MS2 can be readily achieved within 20 s. The inactivation rates are much faster than those achieved on the plate type electrode operated at flow-by mode (five-log inactivation after 5-10 min) (Yang et al. 2014; Huang et al. 2016).

Example 12: Exemplary Applications: Treatment of Per- and Poly-Fluorinated Alkyl Substances

(108) The application of NAT/AT REM on the electrochemical treatment of per- and poly-fluorinated alkyl substances (PFAS) was developed by the Yang group at Clarkson University. Preliminary tests were conducted to treat PFAS in landfill leachate (provided by Waste Management). The REM reactor was filled with 250 mL of leachate. A NAT/AT REM was located in the center of the reactor, and a Ti mesh cathode was placed peripherally around the anode. Leachate was pumped out from the filter anode and then recirculated back to the reactor at a flow rate of 100 mL/min. DC current of 1 A (j=10 mA/cm.sup.2) was applied to the system, resulting in a cell voltage of 5 V. Anode potential was 4 V.sub.RHE, which is sufficiently high to catalyze the oxidation of PFAS. As shown in FIGS. 25B-25C, more than 90% removal of PFOA and complete removal of PFOS were achieved at a residence time of 0.5 h. It is also found that 82-91% of C.sub.4-C.sub.7 PFCAs were removed after 1 h electrolysis. The removal efficiencies did not depend on carbon-chain length. PFAS precursors, EtFOSAA and MeFOSAA, were largely removed after 0.5 h, indicating that EOF is also efficient for the elimination of precursors.

Example 13: Exemplary Applications: Stability Under High Anodic Potentials

(109) The NAT/AT REM demonstrates superior stability under high anodic potential. A continuous electrolysis test at 1 A shows that the anodic potential can be maintained above 4.5 V.sub.RHE for 2000 h with no sign of electrode impairment. In contrast, a plate-type electrode with only NAT coating was reported to be deactivated within 10 h under the same test condition (Yang et al. 2014).

REFERENCES

(110) Huang X, Qu Y, Cid C A, et al (2016) Electrochemical disinfection of toilet wastewater using wastewater electrolysis cell. Water Res 92:164-172. https://doi.org/10.1016/j.watres.2016.01.040 Yang S Y, Kim D, Park H (2014) Shift of the Reactive Species in the Sb-SnO2-Electrocatalyzed Inactivation of E. coli and Degradation of Phenol: Effects of Nickel Doping and Electrolytes. Environ Sci Technol 48:2877-2884. https://doi.org/10.1021/es404688z

Example 14: Overview of Advantageous Over Certain Art

(111) The term reactive electrochemical membrane (REM) was proposed by (Zaky and Chaplin 2013), in which REM was produced by the higher temperature reduction of TiO.sub.2 filter to the Ti.sub.4O.sub.7 filter. In the following years, this group from the University of Illinois in Chicago further developed the other approaches to synthesize REM (e.g., sintering Ti.sub.4O.sub.7 powders to porous media)(Jing et al. 2018). The preparation of Ti.sub.4O.sub.7 REM requires high temperature (1000° C.) and pure H.sub.2. The NAT/AT REM disclosed herein can be prepared at a lower temperature range (e.g., 600° C.) under the air atmosphere and ambient pressure.

(112) (Li et al. 2016; Yang et al. 2018; Zhou et al. 2019) reported the dip-coating methods to coat Sb—SnO2 onto the Ti filter. Advantageous of methods presented herein include: 1) use of flammable alcohol such as methanol or ethanol to reduce the surface tension of the coating solution and allow flame-combustion reactions to shorten synthesis; 2) directly heated at high temperature the filter coated with organic precursors without the drying step.

(113) (Yang et al. 2014) reported the electrochemical production of ozone on Ni—Sb—SnO2 (NAT) coated plate electrodes, not on a REM.

(114) The Nate Lewis group at Caltech reported a NiSb.sub.2O.sub.x coated plate-type electrode (Moreno-Hernandez et al. 2019). The catalyst composition, electrode configuration, and application are completely different from the NAT/AT REM disclosed herein.

(115) The plate type electrode operated at flow-by mode has poor mass transfer efficiency than the REM operated at flow-through mode. (Trellu et al. 2018) summarized that the mass transfer rate constant (km) of Ti.sub.4O.sub.7 REM is almost two orders of magnitude higher than that of plate type electrodes (1.4×10.sup.−4 vs. 5.8×10.sup.−6 m/s).

REFERENCES

(116) Jing Y, Almassi S, Mehraeen S, et al (2018) The roles of oxygen vacancies, electrolyte composition, lattice structure, and doping density on the electrochemical reactivity of Magnéli phase TiO2 anodes. J Mater Chem A 6:23828-23839. https://doi.org/10.1039/C8TA03719A Li D, Tang J, Zhou X, et al (2016) Electrochemical degradation of pyridine by Ti/SnO2-Sb tubular porous electrode. Chemosphere 149:49-56. https://doi.org/10.1016/j.chemosphere.2016.01.078 Lin H, Niu J, Liang S, et al (2018) Development of macroporous Magnéli phase Ti4O7 ceramic materials: As an efficient anode for mineralization of poly- and perfluoroalkyl substances. Chem Eng J 354:1058-1067. https://doi.org/10.1016/j.cej.2018.07.210 Moreno-Hernandez I A, Brunschwig B S, Lewis N S (2019) Crystalline nickel, cobalt, and manganese antimonates as electrocatalysts for the chlorine evolution reaction. Energy Environ Sci 12:1241-1248. https://doi.org/10.1039/C8EE03676D Trellu C, Chaplin B P, Coetsier C, et al (2018) Electro-oxidation of organic pollutants by reactive electrochemical membranes. Chemosphere 208:159-175. https://doi.org/10.1016/j.chemosphere.2018.05.026 Yang K, Lin H, Liang S, et al (2018) A reactive electrochemical filter system with an excellent penetration flux porous Ti/SnO 2-Sb filter for efficient contaminant removal from water. RSC Adv 8:13933-13944. https://doi.org/10.1039/C8RA00603B Yang S Y, Kim D, Park H (2014) Shift of the Reactive Species in the Sb—SnO2-Electrocatalyzed Inactivation of E. coli and Degradation of Phenol: Effects of Nickel Doping and Electrolytes. Environ Sci Technol 48:2877-2884. https://doi.org/10.1021/es404688z Zaky A M, Chaplin B P (2013) Porous Substoichiometric TiO2 Anodes as Reactive Electrochemical Membranes for Water Treatment. Environ Sci Technol 47:6554-6563. https://doi.org/10.1021/es401287e Zaky A M, Chaplin B P (2014) Mechanism of p-Substituted Phenol Oxidation at a Ti4O7 Reactive Electrochemical Membrane. Environ Sci Technol 48:5857-5867. https://doi.org/10.1021/es5010472 Zhou C, Wang Y, Chen J, et al (2019) High-efficiency electrochemical degradation of antiviral drug abacavir using a penetration flux porous Ti/SnO2-Sb anode. Chemosphere 225:304-310. https://doi.org/10.1016/j.chemosphere.2019.03.036

Further Examples

(117) Further useful descriptions and embodiments may be found in U.S. Patent Publication No. 2018/0057952 (Hoffman et al., filed Aug. 22, 2017) and U.S. Pat. No. 10,059,607 (Hoffman et al., filed Jan. 28, 2015), each of which is incorporated herein by reference in its entirety to the extent not inconsistent herewith.

(118) Other useful descriptions, such pertain to applications and descriptions of optional embodiments are found the following publications, each of which is incorporated herein by reference in its entirety to the extent not inconsistent herewith: Barry et al. (U.S. Patent Publication No. 2011/0180423), Zhang et al. (U.S. Patent Publication No. 2017/0334751), Chaplin et al. (U.S. Patent Publication No. 2017/0152163), Huang et al. (U.S. Patent Publication No. 2019/0185351), Zhang et al. (U.S. Patent Publication No. 2019/0345044), and Mullen et al. (U.S. Patent Publication No. 2019/0284066).

STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS

(119) All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference, to the extent each reference is at least partially not inconsistent with the disclosure in this application (for example, a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference).

(120) The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention and it will be apparent to one skilled in the art that the present invention may be carried out using a large number of variations of the devices, device components, methods steps set forth in the present description. As will be obvious to one of skill in the art, methods and devices useful for the present methods can include a large number of optional composition and processing elements and steps.

(121) As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural reference unless the context clearly dictates otherwise. Thus, for example, reference to “a cell” includes a plurality of such cells and equivalents thereof known to those skilled in the art. As well, the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising”, “including”, and “having” can be used interchangeably. The expression “of any of claims XX-YY” (wherein XX and YY refer to claim numbers) is intended to provide a multiple dependent claim in the alternative form, and in some embodiments is interchangeable with the expression “as in any one of claims XX-YY.”

(122) The term “and/or” is used herein, in the description and in the claims, to refer to a single element alone or any combination of elements from the list in which the term and/or appears. In other words, a listing of two or more elements having the term “and/or” is intended to cover embodiments having any of the individual elements alone or having any combination of the listed elements. For example, the phrase “element A and/or element B” is intended to cover embodiments having element A alone, having element B alone, or having both elements A and B taken together. For example, the phrase “element A, element B, and/or element C” is intended to cover embodiments having element A alone, having element B alone, having element C alone, having elements A and B taken together, having elements A and C taken together, having elements B and C taken together, or having elements A, B, and C taken together.

(123) When a group of substituents is disclosed herein, it is understood that all individual members of that group and all subgroups, including any isomers, enantiomers, and diastereomers of the group members, are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. When a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination. Additionally, unless otherwise specified, all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure. For example, it will be understood that any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium. Isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use. Methods for making such isotopic variants are known in the art. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently.

(124) Certain molecules disclosed herein may contain one or more ionizable groups [groups from which a proton can be removed (e.g., —COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein. With regard to salts of the compounds herein, one of ordinary skill in the art can select from among a wide variety of available counterions those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.

(125) Every device, system, electrode, formulation, combination of components, or method described or exemplified herein can be used to practice the invention, unless otherwise stated.

(126) Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. It will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein.

(127) All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein, if needed, to exclude specific embodiments that are in the prior art. For example, when composition of matter are claimed, it should be understood that compounds known and available in the art prior to Applicant's invention, including compounds for which an enabling disclosure is provided in the references cited herein, are not intended to be included in the composition of matter claims herein.

(128) As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of” excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms “comprising”, “consisting essentially of” and “consisting of” may be replaced with either of the other two terms. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.

(129) One of ordinary skill in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such materials and methods are intended to be included in this invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.