ELECTROCATALYSTS AND METHODS OF MAKING AND USING SAME
20250341008 ยท 2025-11-06
Inventors
Cpc classification
H01M4/9033
ELECTRICITY
C25B11/093
CHEMISTRY; METALLURGY
International classification
C25B11/093
CHEMISTRY; METALLURGY
Abstract
Described herein are catalysts, methods of making same, and methods of using same. The catalysts are stable and especially useful for catalyzing anodic reactions in acidic electrolytes.
Claims
1. An electrocatalyst, comprising: a first-row transition metal; antimony; a noble metal; and oxygen.
2. The electrocatalyst according to claim 1, wherein the first-row transition metal is selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and combinations thereof.
3. The electrocatalyst according to claim 1, wherein the noble metal is selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), gold (Ag), and combinations thereof.
4. The electrocatalyst according to claim 1, wherein the noble metal comprises ruthenium (Ru) and/or iridium (Ir).
5. The electrocatalyst according to claim 1, wherein the electrocatalyst has a chemical composition according to Formula I: ##STR00003## wherein: M.sup.N represents the noble metal; M.sup.T represents the first-row transition metal; w is in a range of from about 0.05 to about 0.90; x is in a range of from about 0.05 to about 0.90; y is in a range of from about 0.05 to about 0.90; and z is in a range of from about 0.5 to about 2.5.
6. The electrocatalyst according to claim 1, wherein the electrocatalyst has a rutile crystalline structure.
7. The electrocatalyst according to claim 1, wherein the electrocatalyst is configured for catalysis of an anodic reaction in an acidic electrolyte.
8. The electrocatalyst according to claim 1, wherein the anodic reaction is selected from the group consisting of the oxygen evolution reaction, the chlorine evolution reaction, alcohol oxidations, and combinations thereof.
9. The electrocatalyst according to claim 1, wherein the acidic electrolytes are selected from the group consisting of inorganic acids, organic acids, acidic polymers, and combinations thereof.
10. A system comprising the electrocatalyst according to claim 1, wherein the system is selected from the group consisting of proton-exchange membrane electrolyzers, electrochemical carbon capture systems, oxygen generators, metal-air batteries, electro-synthesis devices, chlor-alkali processes, and combinations thereof.
11. A method of making an electrocatalyst, comprising: a first-row transition metal; antimony; a noble metal; and oxygen, the method comprising: incorporating the noble metal into a precursor framework comprising the first-row transition metal, antimony, and oxygen.
12. The method according to claim 11, further comprising purifying the electrocatalyst.
13. The method according to claim 12, wherein the purifying comprises a technique selected from the group consisting of washing, centrifuging, sonication, and combinations thereof.
14. The method according to claim 11, wherein the electrocatalyst has a rutile crystalline structure.
15. The method according to claim 11, wherein the incorporating is achieved via a molten salt synthesis method.
16. A method of using an electrocatalyst, comprising: a first-row transition metal; antimony; a noble metal; and oxygen, the method comprising catalyzing an industrial application with the electrocatalyst.
17. The method according to claim 16, wherein catalyzing the industrial application comprises catalyzing an anodic reaction in an acidic electrolyte.
18. The method according to claim 16, wherein the acidic electrolyte is selected from the group consisting of inorganic acids, organic acids, acidic polymers, and combinations thereof.
19. The method according to claim 16, wherein the anodic reaction is selected from the group consisting of the oxygen evolution reaction, the chlorine evolution reaction, alcohol oxidations, and combinations thereof.
20. The method according to claim 16, wherein the electrocatalyst has a rutile crystalline structure.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0011] The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
[0012] These and other features, aspects, and advantages of the present disclosure will become better understood when the following detailed description is read with reference to the accompanying drawings. These drawings are exemplary and are not to be construed as limiting.
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[0060] Unless otherwise indicated, the drawings provided herein are meant to illustrate features of embodiments of the disclosure. These features are believed to be applicable in a wide variety of systems comprising one or more embodiments of the disclosure. As such, the drawings are not meant to include all conventional features known by those of ordinary skill in the art to be required for the practice of the embodiments disclosed herein.
DETAILED DESCRIPTION
[0061] The present disclosure incorporates the development and validation of scalable electrocatalyst materials for the OER, a critical component of the generation of H.sub.2, and the development of models of intermediate binding energies that are consistent with experimental measurements of electrochemical activity, thereby lending insight into reaction pathways.
[0062] It has been discovered that a transition metal doped antimonate may be used as a support for noble metal active sites, in order to maintain the rutile crystal structure and result in a stable and active low noble metal OER electrocatalyst.
[0063] Disclosed herein is a class of materials that exhibit high activity towards anodic reactions and high stability in acid.
[0064] In one aspect, the present disclosure provides an electrocatalyst comprising a first-row transition metal, antimony, a noble metal, and oxygen.
[0065] In one embodiment, the first-row transition metal is selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and combinations thereof.
[0066] In another embodiment, the noble metal is selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), gold (Ag), and combinations thereof. In some embodiments, the noble metal comprises ruthenium (Ru) and/or iridium (Ir).
[0067] In one aspect, the electrocatalyst has a chemical composition according to Formula I:
##STR00001## [0068] wherein: [0069] M.sup.N represents the noble metal; [0070] M.sup.T represents the first-row transition metal; [0071] w is in a range of from about 0.05 to about 0.90; [0072] x is in a range of from about 0.05 to about 0.90; [0073] y is in a range of from about 0.05 to about 0.90; and [0074] z is in a range of from about 0.5 to about 2.5.
[0075] As used herein, these ranges incorporate all intermediate values between the recited endpoints. For example, a range between 0.05 and 0.2
[0076] In one aspect, w+x+y=1.0.
[0077] In one aspect, w, x, and y are each individually at least 0.05, at least 0.06, at least 0.07, at least 0.08, at least 0.09, at least 0.10, at least 0.11, at least 0.12, at least 0.13, at least 0.14, at least 0.15, at least 0.16, at least 0.17, at least 0.18, at least 0.19, at least 0.20, at least 0.21, at least 0.22, at least 0.23, at least 0.24, at least 0.25, at least 0.26, at least 0.27, at least 0.28, at least 0.29, at least 0.30, at least 0.31, at least 0.32, at least 0.33, at least 0.34, at least 0.35, at least 0.36, at least 0.37, at least 0.38, at least 0.39, at least 0.40, at least 0.41, at least 0.42, at least 0.43, at least 0.44, at least 0.45, at least 0.46, at least 0.47, at least 0.48, at least 0.49, at least 0.50, at least 0.51, at least 0.52, at least 0.53, at least 0.54, at least 0.55, at least 0.56, at least 0.57, at least 0.58, at least 0.59, at least 0.60, at least 0.61, at least 0.62, at least 0.63, at least 0.64, at least 0.65, at least 0.66, at least 0.67, at least 0.68, at least 0.69, at least 0.70, at least 0.71, at least 0.72, at least 0.73, at least 0.74, at least 0.75, at least 0.76, at least 0.77, at least 0.78, at least 0.79, at least 0.80, at least 0.81, at least 0.82, at least 0.83, at least 0.84, at least 0.85, at least 0.86, at least 0.87, at least 0.88, or at least 0.89.
[0078] In one aspect, w, x, and y are each individually at most 0.06, at most 0.07, at most 0.08, at most 0.09, at most 0.10, at most 0.11, at most 0.12, at most 0.13, at most 0.14, at most 0.15, at most 0.16, at most 0.17, at most 0.18, at most 0.19, at most 0.20, at most 0.21, at most 0.22, at most 0.23, at most 0.24, at most 0.25, at most 0.26, at most 0.27, at most 0.28, at most 0.29, at most 0.30, at most 0.31, at most 0.32, at most 0.33, at most 0.34, at most 0.35, at most 0.36, at most 0.37, at most 0.38, at most 0.39, at most 0.40, at most 0.41, at most 0.42, at most 0.43, at most 0.44, at most 0.45, at most 0.46, at most 0.47, at most 0.48, at most 0.49, at most 0.50, at most 0.51, at most 0.52, at most 0.53, at most 0.54, at most 0.55, at most 0.56, at most 0.57, at most 0.58, at most 0.59, at most 0.60, at most 0.61, at most 0.62, at most 0.63, at most 0.64, at most 0.65, at most 0.66, at most 0.67, at most 0.68, at most 0.69, at most 0.70, at most 0.71, at most 0.72, at most 0.73, at most 0.74, at most 0.75, at most 0.76, at most 0.77, at most 0.78, at most 0.79, at most 0.80, at most 0.81, at most 0.82, at most 0.83, at most 0.84, at most 0.85, at most 0.86, at most 0.87, at most 0.88, at most 0.89, or at most 0.90.
[0079] In one aspect, z is at least 0.5, at least 1.0, at least 1.5, or at least 2.0. In one aspect, z is at most 1.0, at most 1.5, at most 2.0, or at most 2.5.
[0080] In one aspect, the electrocatalyst has a rutile crystalline structure.
[0081] In one aspect, the electrocatalyst is configured for catalysis of an anodic reaction in an acidic electrolyte. In one aspect, the anodic reaction is selected from the group consisting of the oxygen evolution reaction, the chlorine evolution reaction, alcohol oxidations, and combinations thereof. In one aspect, the acidic electrolytes are selected from the group consisting of inorganic acids, organic acids, acidic polymers, and combinations thereof.
[0082] A system comprising the electrocatalyst according to claim 1, wherein the system is selected from the group consisting of proton-exchange membrane electrolyzers, electrochemical carbon capture systems, oxygen generators, metal-air batteries, electro-synthesis devices, chlor-alkali processes, and combinations thereof.
[0083] These electrocatalysts are oxides that exhibit nanoscale crystalline structures, conductivity, and high activity towards anodic reactions in acidic electrolytes. Low amounts of iridium or ruthenium are needed to synthesize them, and they exhibit long-term operational stability.
[0084] The electrocatalysts provided herein exhibit two key properties compared to state-of-the-art electrocatalysts such as iridium oxide or ruthenium oxide. Their composition greatly reduces the amount of iridium or ruthenium needed to achieve similar performance metrics as pure noble metal oxides, and their structure leads to enhanced stability compared to iridium oxide or ruthenium oxide. The materials are active for reactions such as the oxygen evolution reaction and the chloride evolution reaction (see, e.g.,
[0085] Another aspect of the present disclosure provides methods of making said electrocatalyst.
[0086] The electrocatalysts provided herein can be made with any method that brings the constituent elements in close proximity and allows them to react. In some embodiments, the methods further comprise heating the constituent elements or providing chemical energy via other means to accelerate the reaction. Suitable examples of such means include, but are not limited to, annealing salts of the constituent elements in an oxygen atmosphere, annealing of metal or oxide films of the constituent elements, or annealing physical mixtures of the constituent oxides.
[0087] In another aspect, the present disclosure provides a method of making an electrocatalyst comprising a first-row transition metal, antimony, a noble metal, and oxygen. The method comprises incorporating the noble metal into a precursor framework comprising the first-row transition metal, antimony, and oxygen.
[0088] In one aspect, the method further comprises purifying the electrocatalyst.
[0089] In one aspect, the purifying comprises a technique selected from the group consisting of washing, centrifuging, sonication, and combinations thereof.
[0090] In one aspect, the electrocatalyst has a rutile crystalline structure.
[0091] In one aspect, the incorporating is achieved via a molten salt synthesis method. The molten salt synthetic method includes loading alkali metal salts or alkali earth metal with chemical precursors and annealing under high temperatures.
[0092] In yet another aspect, the present disclosure provides methods of using the provided electrocatalysts in industrial applications including, but not limited to, (i) as proton-exchange membrane electrolyzers; (ii) electrochemical carbon capture systems; (iii) oxygen generations; (iv) metal-air batteries; (v) electro-synthesis devices; (vi) chlor-alkali processes, and the like.
[0093] In yet another aspect, the present disclosure provides a method of using an electrocatalyst, comprising: a first-row transition metal; antimony; a noble metal; and oxygen. The method comprises catalyzing an industrial application with the electrocatalyst.
[0094] In one aspect, catalyzing the industrial application comprises catalyzing an anodic reaction in an acidic electrolyte. In one aspect, the acidic electrolyte is selected from the group consisting of inorganic acids, organic acids, acidic polymers, and combinations thereof. In one aspect, the anodic reaction is selected from the group consisting of oxygen evolution reaction, the chlorine evolution reaction, alcohol oxidations, and combinations thereof.
EXAMPLES
[0095] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. The starting material for the following Examples may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples. It also is understood that any numerical range recited herein includes all values from the lower value to the upper value. For example, if a range is stated as 10-50, it is intended that values such as 12-30, 20-40, or 30-50, etc., are expressly enumerated in this specification. These are only examples of what is specifically intended, and all possible combinations of numerical values between and including the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
Example 1. Initial Catalyst Results
[0096] To synthesize nanocrystals in accordance with the present disclosure, proposed is a molten salt synthetic method (
[0097] High-resolution TEM images show that the synthesized noble metal MnSb.sub.2O.sub.x particles are crystalline and that the lattice planes are clearly visible (
[0098] To further characterize the chemical makeup of the synthesized nanocrystals XPS was utilized. For the Ir.sub.0.25Mn.sub.0.25Sb.sub.0.5O.sub.x sample the Ir 4f region (
[0099] It was hypothesized that the noble metal MnSb.sub.2O.sub.x will maintain an electrochemical activity that is comparable to that of a pure noble metal while greatly reducing the amount of noble metal present in the material. Preliminary data indicates that the synthesized noble metal MnSb.sub.2O, is highly active and comparable to that of the pure noble metal oxides (
[0100] For these catalysts to be useful in an industrial setting they must be stable under relevant operating conditions for extended periods. One objective is to demonstrate the stability of the electrocatalysts under operation in a proton exchange membrane (PEM) electrolyzer (
[0101] The chronopotentiometry data for Ir.sub.0.1Mn.sub.0.3Sb.sub.0.6O.sub.2 shows stability for 700 hours at a current density of 250 mA cm.sup.2 and an increase of approximately 20-30 mV was seen, further showing the high level of stability (
Example 2. Manganese Iridium Antimony Oxide (MISO) and Manganese Ruthenium Antimony Oxide (MRSO) Nanocrystals
Synthesis.
[0102] Manganese-iridium antimony oxide (MISO) and manganese-ruthenium antimony oxide (MRSO) nanocrystals were synthesized using a molten salt synthesis method. A high-form porcelain crucible was loaded with approximately 4.55 g of NaCl followed by 400 mM Na.sub.2SO.sub.4 (500 L), 80 mM NMCl.sub.2 (NM=Ru, Ir) (500 L), and specific volumes of 400 mM MnCl.sub.2 and 320 mM SbCl.sub.3 corresponding to specific noble metal loadings (10%, 25%, 50%, 75%). Specifically, 300, 100, 33, and 11 L of MnCl.sub.2 and 750, 250, 83, and 28 L of SbCl.sub.3 were added to obtain noble metal loadings of 10, 25, 50, and 75%, respectively. The mixture was stirred until homogenous and heated to 500 or 700 C. for 1 hour, with a temperature increase rate of 20 C. min.sup.1. The reaction mixture was cooled to room temperature and the contents were washed with ultrapure water (35 mL) followed by centrifugation to recollect the product. 2 M HCl (1 mL) was added to the nanopowder and heated to 90 C. for 1 hr in a hot water bath to remove impurities. The product was recollected again through centrifugation at 6000 RPM for 2 min and washed with IPA (1 mL) followed by centrifugation to recollect product. The resulting black powder was allowed to dry under vacuum.
Characterization.
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[0105] The electrochemical properties of MISO and MRSO nanocrystals synthesized at 500 C. and 700 C. were evaluated at a catalyst loading of 125 g cm.sup.2. MISO-75 nanocrystals synthesized and IrO.sub.2 exhibited improved overpotential at a synthesis temperature of 500 C. compared to 700 C. The activity improvements could be attributed to surface area enhancements as indicated by similar intrinsic overpotentials. MISO nanocrystals synthesized with an initial iridium amount of 25% and 50% exhibited similar overpotentials and intrinsic overpotentials. The Tafel slope of MISO nanocrystals increased as synthesis temperature increased for all initial iridium amounts expect for 10% iridium. MRSO nanocrystals exhibited substantial differences in activity trends as synthesis temperature decreased from 700 C. to 500 C. MRSO nanocrystals synthesized at an initial ruthenium amount of 50% and a synthesis temperature of 700 C. exhibited improved activity towards the OER compared to RuO.sub.2 in extrinsic activity, intrinsic activity, and Tafel slope measurements. Nanocrystals of MRSO synthesized at 500 C. exhibited decreased extrinsic and extrinsic activity compared to RuO.sub.2 synthesized at 500 C. Overall, the results indicate that nanocrystals synthesized at 700 C. result in electrocatalysts that exhibit improved activity due to synergistic interactions between manganese antimony oxide (MnSbO.sub.x) and noble metal oxides.
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[0107] The performance of MISO nanocrystals for PEM electrolysis was determined as shown in
[0108] The stability number, which corresponds to the moles of O.sub.2 evolved per moles of Ir detected, was determined to be 1.0710.sup.9 for the MISO-25 electrolyzer for the overall dissolution study. The dissolution rates of Ir, Mn, and Sb were found to decrease with time, with the Ir dissolution rate being 0.613 picomoles per hour from 181 to 234 hours of operation, corresponding to a stability number of 3.4310.sup.9 in this time range. The reported stability number for IrO.sub.2-based PEM electrolyzers is 6.7310.sup.8, indicating that MISO-25 could exhibit an 80% reduction in iridium loss during operation.
DISCUSSION
[0109] The high synthesis temperatures necessary to crystallize transition metal antimonates has typically limited studies to thin films or microcrystalline powders. This work demonstrates an approach to synthesized nanocrystalline samples of transition metal antimonates with a salt matrix that prevents nanocrystal aggregation, which enables efficient utilization of scarce elements and the study of nanoscale effects that could impact electrocatalyst activity and stability. In general, the morphology of MISO and MRSO nanocrystals resulted in high-aspect ratio structures that preferentially expose (110) crystallographic facets of a rutile-type structure.
[0110] Noble metal incorporation resulted in uniformly dispersed Ir or Ru in the nanocrystalline lattice, which could result in Ir or Ru with neighboring Mn and Sb atoms that substantially influence catalytic activity. Changes in intrinsic overpotential and Tafel slope for MISO and MRSO indicate that the catalytic active site for OER is substantially affected by Mn and Sb incorporation.
[0111] Substantial enrichment of noble metals was observed in the synthesized catalysts compared to the elemental ratios of starting synthesis reagents. In general, noble metal oxides can crystallize at a substantially lower temperature compared to manganese antimony oxide. The present synthesis procedure involves exposing synthesized samples to acidic conditions prior to testing to remove amorphous impurities, which could result in the removal of amorphous MnSbO.sub.x from the catalyst ensemble. The results indicate that careful analysis of elemental composition with materials characterization methods is necessary to elucidate precise compositions for TMA electrocatalysts.
[0112] In general, electrocatalyst that reduce iridium utilization often suffer from decreased activity due to dilution of OER active sites in an OER-inactive matrix. Prior work has shown that manganese antimonate films exhibit moderate activity towards the OER, suggesting that this moderate activity amplifies the activity if Ir-based active sites compared to inactive materials such as TiO.sub.2.
[0113] In summary, manganese iridium antimony oxide nanoparticles were successfully synthesized as a low-iridium electrocatalyst. 25-MISO-700 C. exhibited a low overpotential of 3164 mV at 10 mA cm.sup.2 with an excellent mass activity. This increase in activity is attributed to an improvement in the intrinsic stability of the active sites. It also exhibited a high level of stability under operation maintaining stability at a current density of 250 mA cm.sup.2. Overall, the good activity and excellent stability make the MISO catalysts an efficient and stable low iridium substitute as an electrocatalyst for the OER in acidic conditions. These findings show that low noble metal TMAs are promising OER electrocatalysts and can be successfully implemented into MEAs.
CONCLUSIONS
[0114] Overall, a low noble metal electrocatalyst that exhibits improved activity and stability for the oxygen evolution reaction compared to its pure noble metal counterparts was developed. TMA materials could allow for the next-generation of electrocatalyst to be developed.
Embodiments
[0115] Further aspects of the invention are provided by the subject matter of the following clauses. These clauses may be combined in any permutation or combination. [0116] 1. An electrocatalyst, comprising: [0117] a first-row transition metal; [0118] antimony; [0119] a noble metal; and [0120] oxygen. [0121] 2. The electrocatalyst according to the preceding clause, wherein the first-row transition metal is selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and combinations thereof. [0122] 3. The electrocatalyst according to any preceding clause, wherein the noble metal is selected from the group consisting of ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (Ir), platinum (Pt), gold (Ag), and combinations thereof. [0123] 4. The electrocatalyst according to any preceding clause, wherein the noble metal comprises ruthenium (Ru) and/or iridium (Ir). [0124] 5. The electrocatalyst according to any preceding clause, wherein the electrocatalyst has a chemical composition according to Formula I:
##STR00002## [0125] wherein: [0126] M.sup.N represents the noble metal; [0127] M.sup.T represents the first-row transition metal; [0128] w is in a range of from about 0.05 to about 0.90; [0129] x is in a range of from about 0.05 to about 0.90; [0130] y is in a range of from about 0.05 to about 0.90; and [0131] z is in a range of from about 0.5 to about 2.5. [0132] 6. The electrocatalyst according to any preceding clause, wherein the electrocatalyst has a rutile crystalline structure. [0133] 7. The electrocatalyst according to any preceding clause, wherein the electrocatalyst is configured for catalysis of an anodic reaction in an acidic electrolyte. [0134] 8. The electrocatalyst according to any preceding clause, wherein the anodic reaction is selected from the group consisting of the oxygen evolution reaction, the chlorine evolution reaction, alcohol oxidations, and combinations thereof. [0135] 9. The electrocatalyst according to any preceding clause, wherein the acidic electrolytes are selected from the group consisting of inorganic acids, organic acids, acidic polymers, and combinations thereof. [0136] 10. A system comprising the electrocatalyst according to any preceding clause, wherein the system is selected from the group consisting of proton-exchange membrane electrolyzers, electrochemical carbon capture systems, oxygen generators, metal-air batteries, electro-synthesis devices, chlor-alkali processes, and combinations thereof. [0137] 11. A method of making an electrocatalyst, comprising: [0138] a first-row transition metal; [0139] antimony; [0140] a noble metal; and [0141] oxygen, [0142] the method comprising: [0143] incorporating the noble metal into a precursor framework comprising the first-row transition metal, antimony, and oxygen. [0144] 12. The method according to the preceding clause, further comprising purifying the electrocatalyst. [0145] 13. The method according to any preceding clause, wherein the purifying comprises a technique selected from the group consisting of washing, centrifuging, sonication, and combinations thereof. [0146] 14. The method according to any preceding clause, wherein the electrocatalyst has a rutile crystalline structure. [0147] 15. The method according to any preceding clause, wherein the incorporating is achieved via a molten salt synthesis method. [0148] 16. A method of using an electrocatalyst, comprising: [0149] a first-row transition metal; [0150] antimony; [0151] a noble metal; and [0152] oxygen, [0153] the method comprising catalyzing an industrial application with the electrocatalyst. [0154] 17. The method according to the preceding clause, wherein catalyzing the industrial application comprises catalyzing an anodic reaction in an acidic electrolyte. [0155] 18. The method according to any preceding clause, wherein the acidic electrolyte is selected from the group consisting of inorganic acids, organic acids, acidic polymers, and combinations thereof. [0156] 19. The method according to any preceding clause, wherein the anodic reaction is selected from the group consisting of the oxygen evolution reaction, the chlorine evolution reaction, alcohol oxidations, and combinations thereof. [0157] 20. The method according to any preceding clause, wherein the electrocatalyst has a rutile crystalline structure.
Definitions
[0158] For the purposes of promoting an understanding of the principles of the present disclosure, reference will now be made to preferred embodiments and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the disclosure is thereby intended, such alteration and further modifications of the disclosure as illustrated herein, being contemplated as would normally occur to one skilled in the art to which the disclosure relates.
[0159] As used herein, the term rutile crystalline structure means a crystal structure that is identical to, or substantially similar to, rutile, which has a tetragonal crystal structure characterized by edge-sharing TiO.sub.6 octahedra forming columns, with each oxygen atom shared between two columns and bonded to three Ti atoms.
[0160] Articles a and an are used herein to refer to one or to more than one (i.e. at least one) of the grammatical object of the article. By way of example, an element means at least one element and can include more than one element.
[0161] About is used to provide flexibility to a numerical range endpoint by providing that a given value may be slightly above or slightly below the endpoint without affecting the desired result. In some embodiments, the term about means plus or minus 10% of the value.
[0162] Unless expressly stated to the contrary, or refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). As used herein, and/or refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the lack of combinations where interpreted in the alternative (or).
[0163] As used herein, the terms comprises, comprising, includes, including, has, having, contains, containing, characterized by or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
[0164] The transitional phrase consisting of excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase consisting of appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
[0165] The transitional phrase consisting essentially of is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term consisting essentially of occupies a middle ground between comprising and consisting of.
[0166] Where an invention or a portion thereof is defined with an open-ended term such as comprising, it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms consisting essentially of or consisting of.
[0167] Moreover, the present disclosure also contemplates that in some embodiments, any feature or combination of features set forth herein can be excluded or omitted. To illustrate, if the specification states that a complex comprises components A, B and C, it is specifically intended that any of A, B or C, or a combination thereof, can be omitted and disclaimed singularly or in any combination.
[0168] Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. For example, if a concentration range is stated as 1% to 50%, it is intended that values such as 2% to 40%, 10% to 30%, or 1% to 3%, etc., are expressly enumerated in this specification. These are only examples of what is specifically intended, and all possible combinations of numerical values between and including the lowest value and the highest value enumerated are to be considered to be expressly stated in this disclosure.
[0169] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
[0170] As used herein, references to example embodiment or one embodiment or some embodiments of the present disclosure are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.
[0171] Unless otherwise indicated, approximating language, such as generally, substantially, and about, as used herein indicates that the term so modified may apply to only an approximate degree, as would be recognized by one of ordinary skill in the art, rather than to an absolute or perfect degree. Accordingly, a value modified by a term or terms such as about, approximately, and substantially is not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Additionally, unless otherwise indicated, the terms first, second, etc. are used herein merely as labels, and are not intended to impose ordinal, positional, or hierarchical requirements on the items to which these terms refer. Moreover, reference to, for example, a second item does not require or preclude the existence of, for example, a first or lower-numbered item or a third or higher-numbered item.
[0172] Although specific features of various embodiments of the invention may be shown in some drawings and not in others, this is for convenience only. In accordance with the principles of the invention, any feature of a drawing may be referenced and/or claimed in combination with any feature of any other drawing.
[0173] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims.
[0174] This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.