DETAILED ACTION
Notice of Pre-AIA or AIA Status
1. The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Response to Amendment
2. The applicant’s amendments filed 08 June 2026 have been entered into the record. The applicant’s response is considered fully responsive. The applicant has pointed to ¶39 and ¶90 for support of their amendment to Claim 1. Claim 14 is new. The examiner agrees that no new matter was added with the amendment to Claim 1 nor the addition of new Claim 14. Claims 8, 9, 10, 11, and 12 were previously withdrawn due to an election/restriction. Currently, Claims 1, 2, 3, 4, 5, 7, 13, and 14 are under examination.
Claim Rejections - 35 USC § 103
3. The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
4. The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
5. Claim 1, 2, 3, 4, 5, 7, and 13-14 are rejected under 35 U.S.C. 103 as being unpatentable over Pawar et al. in view of Lu et al. and Liu et al.
Pawar et al. (“Nanoporous CuCo2O4 nanosheets as a highly efficient bifunctional electrode for supercapacitors and water oxidation catalysis,” Appl. Surf. Sci. 2019, 470, 360-367 – previously presented) is directed toward the preparation of ultrathin nanosheets comprised CuCo2O4 (pg. 360: title and abstract). Lu et al. (CN 104134788 B – previously presented) is directed at the preparation and application of a three-dimensional gradient metal hydroxide/oxide electrode material (title). Liu et al. (“Cuprous oxide thin film directly electrodeposited from a simple copper salt on a conductive electrode for efficient oxygen evolution reaction,” Electrochimica Acta 2016, 187, 381-388) is directed toward an OER catalyst (pg. 381: title).
Regarding Claim 1, Pawar et al. discloses a CuCo2O4 nanosheets as a catalyst for water oxidation catalysis (pg. 360: title and abstract; pgs. 360-361: 1. Introduction section; pg. 362: 3. Results and Discussion section & Fig. 2; pg. 364: Fig. 4; and pg. 366: 4. Conclusions section) which is a Cu-X oxide catalyst with X = Co. Additionally, Pawar et al. discloses the catalyst layer is electrodeposited onto a substrate, i.e.: nickel foam (pg. 360: abstract; pgs. 361-362: 2. Experimental section; and pg. 366: 4. Conclusions section). However, Pawar et al. does not explicitly disclose an additional oxide selected from a copper oxide or an X-oxide (e.g.: a cobalt oxide) nor does Pawar et al. disclose a honeycomb-like structure for the 3D nanosheet.
Like Pawar et al., Lu et al. discloses an electrochemically active material (¶4-6): comprising a substrate (i.e.: copper foam) and a catalyst layer (copper cobalt oxide) as per Ex. 7 (¶250-252). Lu et al. further discloses the material has a three-dimensional cellular nanosheet (i.e.: nanosheets in a honey-comb shape) as depicted in Figure 1 (from Ex. 1). Lu et al. and Pawar et al. both use electrodeposition to synthesize mixed copper-cobalt oxides. Lu et al. specifically prepares four different copper (II) nitrate and cobalt(II) nitrate electrolyte baths at 0.50 M total metal ion concentration with the ratios of metal ions of: (i) 0.40 M Cu2+ to 0.10 M Co2+; (ii) 0.38 M Cu2+ to 0.12 M Co2+; (iii) 0.33 M Cu2+ to 0.17 M Co2+; and (iv) r0.25 M Cu2+ to 0.25 M Co2+ (¶252). Lu et al. explains electrodeposition from the electrolyte forms a mixture of hydroxides, which is then annealed to form a gradient metal oxide (¶124 and 252). Lu et at. discloses a catalyst layer that is the Cu-X-oxide where the X is cobalt. Lu et al. further indicates the general form of the gradient oxide has the form CuxCoyO4 (¶252) with the values of x and y satisfying the relationships below:
I.
x: 0 < x < 4
II.
y: 0 < y < 8/3
III.
2x + 3y = 8
Lu et al. further indicates that the content of copper and cobalt in the gradient oxide vary within the thickness of the layer. The concentration of copper oxide is highest at the substrate coating interface transitioning primarily into cobalt oxide at the surface of the oxide layer (¶252). Given the variation in composition of the composite metal oxide, Lu et al. discloses a copper-cobalt oxide phase (i.e.: a Cu-X-oxide phase) in the middle of the catalyst layer, a copper(II) oxide phase near the substrate/catalyst layer interface, and a cobalt oxide (i.e.: X-oxide) near the catalyst layer/air interface.
It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to substitute the catalyst layer composition and substrate taught in Pawar et al. with the complex copper-cobalt oxide layer and the copper foam substrate of Lu et al. with the reasonable expectation of forming an electrode material (i.e.: substrate+catalyst layer) with improved of OER activity as the copper foam has increased electrical conductivity. The preceding case of obviousness is supported by the introduction of Pawar et al. (pg. 360-1) which explains that mixed oxides of copper and cobalt are known to be effective OER catalysts with superior electrochemical activity and electrical conductivity compared to only the monometallic oxides (i.e.: cobalt oxide only). Moreover, thin nanosheets deposited onto foam substrates have the advantages of facile diffusion paths for ions and electrons, large electrochemically active sites at the electrode-electrolyte interface, high electrical conductivity and improved structural stability (pg. 361: 1 Introduction section of Pawar et al.).
The combination of Pawar et al. in view of Lu et al. only discloses the formation of a separate copper(II) oxide phase, not a separate Cu2O (i.e.: cuprous oxide) phase as required by amended Claim 1. Liu et al. is directed toward the electrodeposition of Cu2O for use in OER catalysis. According to the experimental details section on pg. 382 of Liu et al., the Cu2O layer was deposited from a simple copper acetate/sodium acetate electrolyte under mild conditions and dried in air after the deposition was complete. Liu et al. confirmed the identity of Cu2O by XRD (pg. 382: Fig. 1). The amount of charged was modulated to control the reduction of Cu(II) from the electrolyte to form Cu2O deposits and avoid the deposition of metallic copper (pg. 384: Results and Discussion and Fig. 4). The deposited Cu2O is an efficient OER catalyst with low overpotential (Liu et al. pg. 386: Results and Discussion and Fig. 8). Liu et al. further indicates that the electrodeposited Cu2O OER catalyst is formed using a method not requiring templating, surfactant, nor binders (pg. 387: Results and Discussion). The deposited Cu2O material is also a superior catalyst to copper(II) oxide as per the previous work of Liu et al. as the former species has a lower onset potential for oxygen generation. It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed reaction to modify the composite copper cobalt oxide OER catalyst of Pawar et al. and Lu et al. by electrodepositing a discrete Cu2O layer onto the substrate surface prior to electrodepositing the mixed copper-cobalt oxide catalyst layer with the reasonable expectation of improving the OER catalytic activity. The modification of the oxidation state of deposited copper in the catalyst layer to include Cu(I) is expected to improve the OER catalyst efficiency as evidenced by Liu et al. showing Cu(I) is a superior OER catalyst to Cu(II) as per the results and discussion section.
Regarding Claim 2, Pawar et al. in view of Lu et al. and Liu et al. disclose a water electrolysis electrode as per Claim 1 wherein the substrate is a foam material in the form of copper foam in Ex. 7 (Lu et al. ¶250-252).
Regarding Claim 3, Pawar et al. in view of Lu et al. and Liu et al. disclose a water electrolysis electrode as per Claim 1, wherein the substrate is specifically copper foam as taught in Ex. 7 for the preparation of mixed copper-cobalt oxides (Lu et al. ¶250-252).
Regarding Claim 4, Pawar et al. in view of Lu et al. and Liu et al. disclose a water electrolysis electrode of Claim 1, wherein the catalyst layer has a thickness of 400 nm to 3000 nm as supported by the range of 500 nm to 50,000 nm in Lu et al. ¶178 for the thickness of the metal oxide (hydroxide) layer. In Ex. 1 of Lu et al., the specific thickness taught is 900 nm for a catalyst layer comprised of nickel-cobalt oxide (Lu et al. ¶201-203) which is consistent across the other embodiments/examples of Lu et al. including the copper-cobalt oxides of Ex. 7. The deposition of a thin layer of Cu2O directly on top of the substrate surface prior to the electrodeposition of mixed copper-cobalt oxide catalyst would still keep the total catalyst thickness overlapping with the claimed range as the Cu2O film is described as thin film in Liu et al. A prima facie case of obviousness exists when the prior art and the claimed range overlap. See MPEP 2144.05(I) - OVERLAPPING, APPROACHING, AND SIMILAR RANGES, AMOUNTS, AND PROPORTIONS.
Regarding Claim 5, Pawar et al. in view of Lu et al. and Liu et al. disclose a water electrolysis electrode as per Claim 1 above, wherein cobalt is the X in Cu-X oxide and CuxCoyOz satisfies the following criterion: (A) x+y = 3; (B) z =4; (C) x ranges 0.7 to 1.0; and (D) y ranges from 2.0 to 2.3 as evidenced by the example of Cu1Co2O4 as explained in ¶252 of Pawar et al. Given the ranges of x, y, and z in ¶252 of Lu et al., x has a value of 1, y has a value of 2, the sum of x and y is 3, and z has a value of 4. Therefore, a prima facie case of obviousness exists when the chemical formula disclosed in an example in the prior art is contained within claimed range of chemical formulas of the instant application. See MPEP 2144.05(I) - OVERLAPPING, APPROACHING, AND SIMILAR RANGES, AMOUNTS, AND PROPORTIONS.
Regarding Claim 7, Pawar et al. in view of Lu et al. and Liu et al. disclose the water electrolysis electrode of Claim 1, where a unit cell of the three-dimensional honeycomb-like structure has a diameter of 100 nm to 300 nm as evidenced by Figure 1 of Lu et al. (reproduced below). The inset 100 nm x 100 nm white cross when compared to the unit cells in the SEM image show the average diameter of said unit cells of the honeycomb-like structure fall within the claimed range and therefore is a prima facie case of obviousness. See MPEP 2144.05(I) - OVERLAPPING, APPROACHING, AND SIMILAR RANGES, AMOUNTS, AND PROPORTIONS.
[AltContent: textbox ([img-media_image1.png]
Figure 1 from Lu et al. showing structure of deposited catalyst)]
Regarding Claim 13, Pawar et al. in view of Lu et al. and Liu et al. discloses a water electrolysis device comprising, as an anode, the water electrolysis electrode as per Claim 1 above. Specifically, Pawar et al. in view of Lu et al. and Liu et al. discloses the evaluation of oxygen evolution reaction activity of the copper-cobalt oxide/copper (I) oxide catalyst of Claim 1 as the working electrode (i.e.: the anode), a Pt wire as the counter electrode, and an SCE as the reference electrode in an electrolyte of 1.0 M KOH as explained in section 2.3. Electrochemical measurements of Pawar et al. (pg. 361). The oxygen evolution reaction occurs at the anode when hydroxide anion (oxygen is in the negative two oxidation state) and loses two electrons to form molecular dioxygen (oxygen is in the zero oxidation state).
Regarding Claim 14, Pawar et al. in view of Lu et al. and Liu et al. discloses the water electrolysis electrode of Claim 1, wherein the catalyst layer further comprises an X-oxide phase present as a distinct phase separate from the Cu-X oxide phase in the form of Co-oxide. As explained above for the electrodeposition of copper-cobalt oxides, Lu et al. utilized different copper (II) nitrate and cobalt(II) nitrate electrolyte baths compositions (¶252) and electrodeposition from the electrolyte forms a mixture of hydroxides, which is then annealed to form a gradient metal oxide (¶124 and 252). Lu et al. further indicates that the content of copper and cobalt in the gradient oxide vary within the thickness of the layer. The concentration of copper oxide is highest at the substrate coating interface transitioning primarily into cobalt oxide at the surface of the oxide layer (¶252). Given the variation in composition of the composite metal oxide, Lu et al. discloses a cobalt oxide phase nearest the catalyst/air interface (i.e.: an X-oxide phase) and separate a copper-cobalt oxide phase through the remainder of the thickness of the catalyst layer (i.e.: a Cu-X-oxide phase. Therefore, the teachings of Pawar et al. in view of Lu et al. and Liu et al. reads onto the limitations of Claim 14.
Response to Arguments
6. The rejection of Claims 1, 2, 3, 4, 5, 7, and 13 under 35 U.S.C. 103 as being unpatentable over Pawar et al. in view of Lu et al. is withdrawn given the amendment to Claim 1 requiring the formation of copper oxide in the form of Cu2O as part of the catalyst layer of the water electrolysis electrode. The combination of references fails to teach the presence of Cu(I) in the catalyst layer. However, upon further consideration, a new ground(s) of rejection is made in view of Pawar et al., Lu et al., and Liu et al.
7. In order to cure the deficiencies of Pawar et al. and Lu et al. pertaining to the presence of Cu2O in the catalyst layer, the examiner has modified said combination with Liu et al. Liu et al. is directed towards a Cu2O OER catalyst deposited by electrodeposition as explained above. The modification of the catalyst layer of Pawar et al. and Lu et al. with the Cu2O deposit of Liu et al. is reasonably expected to improve the OER catalysis given the beneficial electrochemical performance properties of the Cu2O deposits as explained in Liu et al. This is explained further in the rejection of amended Claim 1 above.
8. The applicant has argued that the instant application (cited as filed), ¶90, FIG. 4, FIG. 5a, and FIG. 5b provide a basis for a catalyst layer comprised of a mixed copper-cobalt oxide (e.g.: Cu0.81Co2.19O4) and a copper oxide (e.g.: Cu2O). The oxidation states of the metal centers are assigned based on XPS data (FIG. 5a, and FIG. 5b). FIG. 2 of the instant application shows EDS mapping data of the deposited catalyst layer illustrating cobalt deficient regions and cobalt-rich regions. The EDS map for copper on FIG. 2 shows the presence of copper is more or less uniformly distributed. The relative ratios of each metal center were determined used the final stoichiometry of the catalyst layer. Given the aforementioned data, the applicant has determined the stoichiometry and single-phase nature of the Cu-X oxide and the Cu-oxide cited in amended Claim 1 in a manner which is analogous to the teachings of Pawar et al., Lu et al., and now Liu et al. Moreover, the instant application and the prior art (i.e.: Pawar et al., Lu et al., and Liu et al.) both disclose the electrodeposition of a copper/cobalt oxide using an aqueous electrolyte of soluble cobalt ions and copper ions followed by a high temperature annealing. Therefore, the methods of depositions, processing, and characterization of the deposited catalysts are substantially similar. The applicant may consider specifically adding electrodeposition bath compositions or method parameters to the claim limitations as possible means to distinguish their alleged invention over the cited prior art.
Request for Information
9. Applicant and the assignee of this application are required under 37 CFR 1.105 to provide the following information that the examiner has determined is reasonably necessary to the examination of this application.
10. In response to this requirement, please provide answers to each of the following interrogatories eliciting factual information:
The instant was application has an effective filing date of 06 September 2019 based on the foreign priority to KR10-2019-0111058. The applicant/inventive entity of the instant application was scheduled to present a paper entitled “Electrochemical Preparation of Copper-Cobalt Oxide Nanosheets Array on Nickel Foam As the Catalyst for Oxygen Evolution Reaction” at the ECS Meeting on 16 May 2018 during the section entitled “OER in Alkaline Media 2.” A copy of this abstract has been included with this office action showing the aforementioned date and time. If this presentation was given, then the contents of the presentation would have been publicly disclosed about 16 months before the effective filing date of the instant application and would fall outside of the §102(b)(1)(A) exception. Was the presentation publicly delivered with a concomitant displaying out content(e.g.: slides or presentation_ at the ECS meeting on 16 May 2018?
In analysis of the publicly disclosed abstract, the examiner has determined that the presentation at the ECS Meeting in 2018 potentially would meet the requirements for prior art for the instant application. The publicly available abstract has been copied below in its entirety. The portions of the abstract most germane to the instant application have been bolded and underlined in the abstract copied below. Is the applicant able to provide a copy of the presentation (e.g.: slide deck) to the examiner for review and determination of relevance as a piece of prior art for the instant application?
Development of sustainable energy has recalled highly efficient energy storage technology because it generates the electricity stochastically from the sources such as solar and wind. The water electrolysis has been considered as the one of the promising options to convert and store electrical energy as the form of hydrogen. However, relatively large overpotential from anodic half reaction, that is, oxygen evolution reaction (OER) has hindered commercial use of hydropower.
The recent studies about OER have focused on finding out non-noble metal catalyst because the RuO2 and IrO2, ideal catalysts for OER, are scarce and expensive. Among the non-noble metal oxides, cobalt (III, IV) oxide has been received great attention since it is anticipated to be second best ideal catalyst for OER from theoretical calculations. With this respect, the number of nano-sized cobalt oxide electrodes with different morphologies have been prepared and utilized as the anode of electrolytic water splitting system.
In this work, copper-cobalt oxides nanosheets catalyst layer was electrochemically prepared on the nickel foam substrate. To achieve nano-porous morphology of deposit, cobalt oxide was co-deposited with copper oxide. The structural and spectroscopic analyses revealed that cobalt-copper oxides nanosheet array consists of mixture of Co3O4 and CuxCo3-xO4. As the catalyst for OER, the resulting catalyst showed exceptional catalytic activity thanks to its nano- to micro-porous structure, which allows facile transport of active species. Furthermore, it showed great long-term stability.
In this presentation, the catalytic activity of cobalt-copper oxides will be discussed in terms of electrochemical properties. In particular, several electrochemical parameters such as anodic Tafel slopes and overpotentials at different current densities will be suggested and compared to that of other nanostructured catalysts reported in literature. Furthermore, the effect co-deposition of copper and cobalt oxides on growth habit of overall deposit and its OER performance will be discussed.
The amended set of claims currently under examination have been copied below. In the examiner’s interpretation of the publicly available abstract, the ECS presentation is germane to Claims 1, 2, 5, 13, and 14. Can the applicant indicate what claims/parts of the claims under examination are linked to the ECS presentation?
Claim 1. (Currently amended) A water electrolysis electrode comprising: an electrode substrate; and a catalyst layer located on the electrode substrate, wherein the catalyst layer comprises:(i) a Cu-X oxide phase; and(ii) a Cu oxide phase present as a distinct phase separate from the Cu-X oxide phase, wherein the Cu oxide phase comprises a Cu2O phase, wherein the catalyst layer has a three-dimensional nanosheet structure, wherein X is one of Co, Mn, Fe, Ni, V, W, Mo, Pt, Ir, Pd and Ru, and wherein the three-dimensional nanosheet structure of the catalyst layer has a three- dimensional honeycomb-like structure.
Claim 2. (Original) The water electrolysis electrode of claim 1, wherein the electrode substrate is in the form of a foam or plate.
Claim 3. (Original) The water electrolysis electrode of claim 1, wherein the electrode substrate comprises at least one of Ni, SUS, Ti, Au, Cu, ITO and FTO.
Claim 4. (Original) The water electrolysis electrode of claim 1, wherein the catalyst layer has a thickness of 400 nm to 3,000 nm.
Claim 5. (Previously presented) The water electrolysis electrode of claim 1, wherein the Cu-X oxide phase is CuxXyOz, wherein x and y satisfy x+y=3, and z is 4.
Claim 7. (Previously presented) The water electrolysis electrode of claim 1, wherein a unit cell of the three-dimensional honeycomb-like structure has a diameter of 100 nm to 300 nm.
Claim 13. (Previously presented) A water electrolysis device comprising, as an anode, the water electrolysis electrode according to claim 1.
Claim 14. (New) The water electrolysis electrode of claim 1, wherein the catalyst layer further comprises an X oxide phase present as a distinct phase separate from the Cu-X oxide phase.
The examiner has a series of specific inquiries directed toward the applicant to better understand the contents of the disclosure of the ECS presentation.
Can the applicant provide details pertaining to the electrolyte bath used to deposit the mixed Cu/Co oxide including metal salts, metal salt concentration, pH, and other bath additives?
Can the applicant provide details around the electrodeposition conditions (e.g.: current density, time, AC/DC) and the curing/annealing conditions?
Can the applicant share any characterization data, e.g.: XRD, XPS, SEM, compositional analysis?
Can the applicant share any structure property relationships?
Can the applicant provide electrochemical characterization of the catalyst for water splitting and/or oxygen evolution reaction?
11. The applicant is reminded that the reply to this requirement must be made with candor and good faith under 37 CFR 1.56. Where the applicant does not have or cannot readily obtain an item of required information, a statement that the item is unknown or cannot be readily obtained may be accepted as a complete reply to the requirement for that item.
Conclusion
12. Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
13. Any inquiry concerning this communication or earlier communications from the examiner should be directed to KEVIN SYLVESTER whose telephone number is 703-756-5536. The examiner can normally be reached Mon - Fri 8:15 AM to 4:30 PM EST.
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/KEVIN SYLVESTER/Examiner, Art Unit 1794
/JAMES LIN/Supervisory Patent Examiner, Art Unit 1794
/PATRICIA MALLARI/Director, Technology Center 1700
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