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 .
Continued Examination Under 37 CFR 1.114
2. A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 09 January 2026 has been entered.
Response to Amendments
3. No changes to the claims were made. Currently, Claims 1, 2, 3, 4, 6, 7, 8, 9, and 10 are pending and under examination in the instant application. Claims 5, 11, 12, and 13 were previously cancelled by the applicant. The applicant has included updated drawing for Fig. 3F as requested by the examiner in the previous office action.
Claim Rejections - 35 USC § 103
4. 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.
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, 8, and 9 are rejected under 35 U.S.C. 103 as being unpatentable over An et al.
An et al. (“One-Step Controllable Synthesis of Catalytic Ni4Mo/MoOx/Cu Nanointerfaces for Highly Efficient Water Reduction,” Adv. Energy Mater. 2019, 9, article 1901454, pg. 1-10 – previously presented) is directed toward alkaline hydrogen evolution (pg. 1: abstract).
Regarding Claim 1, An et al. discloses a method of manufacturing an electrode (e.g.: Cu-supported Ni4Mo/MoOx on pg. 1: abstract) used for water electrolysis (e.g.: Cu-supported Ni4Mo/MoOx showing smallest over potential in 1 M KOH/alkaline H2 evolution on pg. 1 abstract and pg. 9: final paragraph), the method comprising: (i) preparing the catalyst materials including solvent (e.g.: water), a nickel precursor (e.g.: NiCl2‧6H2O), a molybdenum precursor (Na2MoO4‧2H2O), and sodium citrate (e.g.: Na3C6H5O7‧2H2O) according to the experimental section of the supporting information; (ii) preparing an electrode base material (nickel or copper sponge) according to the experimental section of the supporting information; (iii) obtaining a plating solution by dissolving the nickel precursor (e.g.: NiCl2‧6H2O), the molybdenum precursor (Na2MoO4‧2H2O), and the sodium citrate (e.g.: Na3C6H5O7‧2H2O) in the solvent (e.g.: water) according to the experimental section of the supporting information; and (iv) forming a catalyst layer on the surface of the electrode base material by immersing the electrode base material in the plating solution and applying an electric current as described the experimental section of the supporting information by the application of 50 mA/cm2 for 300 s to deposit the Ni4Mo/MoOx catalyst layer on the metal sponge.
An et al. does not teach the sequential addition of the Ni-precursor, sodium citrate, and the Mo-precursor to water as per the claim limitation of Claim 1. However, a prima facie case of obviousness exists regarding the selection in the order of performing process steps (i.e.: the order of the addition of Ni, Mo, and citrate to water to form the plating solution. See MPEP 2144.04(IV): Rationale C – CHANGES IN THE SEQUENCE OF ADDING INGREDIENTS.
Specifically, An et al. depicts an electrodeposition mechanism in the supporting information under the section: “electrodeposition reaction” which proposes the formation of a nickel citrate (i.e.: [NiCit]1-) which is consistent with the explanation for the order of addition as per the claim limitations of Claim 1 and further discussed in the specification of the present application in ¶57-61 as cited in the US Pub. No. 2023/0175153 A1. The instant application proposes that the addition of the nickel precursor followed by the sodium citrate species suppresses the formation of nickel molybdenum oxo clusters. However, An et al. teaches that the formation of said clusters is not an issue when the order of addition of to the solvent is the nickel precursor, the molybdenum precursor, and the sodium citrate (experimental section of the supporting information) given the proposed reaction mechanism below in which nickel and citrate form a complex at a faster rate than the nickel and molybdate.
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Regarding Claim 2, An et al. discloses the method of Claim 1, wherein the preparing of the catalyst materials, the solvent is distilled water, the nickel precursor is nickel chloride dihydrate, the molybdenum precursor is sodium molybdate dihydrate according to the experimental section of the supporting information.
Regarding Claim 3, An et al. discloses the method of Claim 1, wherein the electrode base material is copper foam or nickel foam (pg. 2: Fig. 1A and Supporting Information: Experimental methods).
Regarding Claim 8, An et al. discloses the method of Claim 1 wherein the catalyst layer is alternatively comprised of a nickel-molybdenum alloy (e.g.: Ni4Mo alloy on pg. 4). An et al. discloses the electrodeposition of said material by applying an electric current of a current density 0.1 mA/cm2 to the plating solution comprised of nickel(II) chloride hexahydrate, sodium molybdate dihydrate, and sodium citrate dihydrate as per the experimental section of the supporting information. It has been held that a prima facie case of obviousness exists when a specific example disclosed in the prior art is within the claimed range. See MPEP 2144.05(I) - OVERLAPPING, APPROACHING, AND SIMILAR RANGES, AMOUNTS, AND PROPORTIONS.
Regarding Claim 9, An et al. discloses the method of Claim 8, discussed above, wherein the electroplating is performed for 300 seconds while stirring the solution to form the Ni4Mo alloy on copper foam as per the experimental method section in the supporting information. It has been held that a prima facie case of obviousness exists when a specific example disclosed in the prior art is within the claimed range. See MPEP 2144.05(I).
6. Claim 4 is rejected under 35 U.S.C. 103 as being unpatentable over An et al. as applied to Claim 3 above, and further in view of Sutygina et al.
An et al. (“One-Step Controllable Synthesis of Catalytic Ni4Mo/MoOx/Cu Nanointerfaces for Highly Efficient Water Reduction,” Adv. Energy Mater. 2019, 9, article 1901454, pg. 1-10 – previously presented) is directed toward alkaline hydrogen evolution (pg. 1: abstract). Sutygina et al. (“Manufacturing of Open-Cell Metal Foams by the Sponge Replication Technique,” IOP Conf. Series: Mater. Sci. and Eng. 2020, 882, 012022, pg. 1-10 – previously presented) is directed toward the preparation of open cell metal foams using casting processes (pg. 1: abstract).
Regarding Claim 4, An et al. discloses the method of Claim 3 wherein the electrode base material is ultrasonically cleaned in acetone and treated for 5 minutes in 4 M hydrochloric acid to remove the surface oxide film (pg. 2: Fig. 1A and Supporting Information: Experimental methods). However, An et al. does not describe the molding process used to prepare the nickel or copper foam substrate.
Sutygina et al. discloses a method to prepare copper foam using a template (i.e.: “mold”). Sutygina et al. teaches the use of a polyurethane template foam that is filled with a slurry of copper dispersed using PVA (pg. 6: Section 3.1. Specimen preparation) and then the organic materials were burnt out using an air furnace (pg. 6: Section 3.1. Specimen preparation). The final step of preparation involves processing the metal foam in a reducing atmosphere (Ar+H2) to form a copper foam as indicated by XRD with a porosity of 93% (pg. 7: Section 3.3. Results). The resultant material has high electrical conductivity and high surface area ( pg. 6: Section 2.3.1. Current manufacturing of open-cell metal foams by sponge replication technique).
It would be obvious for one of ordinary skill in the art prior to the effective filing date of the claimed invention to electroplate the plating composition of An et al. on to the copper foam prepared using the molding/template method of Sutygina et al. with the reasonable expectation of forming an effective catalyst layer for water splitting due to the high surface area, high porosity, and high electrical conductivity of the copper foam.
7. Claims 6 and 7 are rejected under 35 U.S.C. 103 as being unpatentable over An et al. as applied to Claim 1 above, and further in view of Chassaing et al.
An et al. (“One-Step Controllable Synthesis of Catalytic Ni4Mo/MoOx/Cu Nanointerfaces for Highly Efficient Water Reduction,” Adv. Energy Mater. 2019, 9, article 1901454, pg. 1-10 – previously presented) is directed toward alkaline hydrogen evolution (pg. 1: abstract). Chassaing et al. (“Mechanism of nickel-molybdenum alloy electrodeposition in citrate electrolytes,” J. Appl. Electrochem. 1989, 19, 839-843 – previously presented) is directed toward the Ni-Mo deposition kinetics (pg. 839: introduction).
Regarding Claim 6, An et al. discloses the method of Claim 1, wherein the obtaining of the plating solution comprises a nickel precursor with a concentration of 0.32 M, a molybdenum precursor concentration of 27 mM, and a sodium citrate concentration of 0.19 M in deionized water as per the experimental method section of the supporting information (the calculation is shown below). The composition of the active species (e.g.: Ni, Mo, and citrate) in the electrolyte are similar to the limitation of Claim 6, but all of said species do not fall within the claimed range (e.g.: Ni and Mo).
Calculation of bath concentrations from An et al.
Ni-precursor: 2.3 g NiCl2‧6H2O (Mol. Weight = 237.69 g/mol) [Wingdings font/0xE8] 9.7 mmol Ni precursor
Mo-precursor: 0.2 g Na2MoO4‧2H2O (Mol. Weight = 241.95 g/mol) [Wingdings font/0xE8] 0.82 mmol Mo precursor
Sodium citrate: 1.7 g Na3C6H5O7‧2H2O (Mol. Weight = 294.10 g/mol) [Wingdings font/0xE8]5.6 mmol sodium citrate
[Ni] precursor = 9.7 mmol/30 mL = 0.32 M
[Mo] precursor = 0.82 mmol/0.030 L = 27 mM
[Sodium citrate] = 5.6 mmol/30 mL = 0.19 M
Chassaing et al. is directed toward the electrodeposition of Ni-Mo species from citrate-based electrolyte with nickel(II) sulfate (i.e.: Ni-precursor) and sodium molybdate (i.e.: Mo-precursor) (pg. 839: abstract and Table 1). Electrolyte A of Chassaing et al. has the electrolyte composition of: 0.2 M nickel precursor, 0.25 sodium citrate, and 7.5 mM molybdenum precursor. Chassaing et al. indicates that the initial deposition from electrolyte yields a stoichiometry of 3 mol Ni to 1 mol Mo with oxygen and hydrogen (pg. 843: discussion). At longer deposition times, Chassaing et al. indicates the formation of a species with the stoichiometry of MoO2Ni4 (pg. 843: discussion). On page 843, Chassaing et al, indicates that Ni-Mo alloys (like deposited in their work) is a catalyst for hydrogen evolution.
The composition of the Ni-Mo species electrodeposited from citrate-based electrolyte in both An et al. and Chassaing et al. are similar and both have activity for promoting the hydrogen evolution reaction. Therefore, it would be obvious to one ordinary skill in the art prior to the effective filing date of the claimed invention to modify the plating bath of An et al. with the concentrations of the Ni-precursor, the Mo-precursor, and the sodium citrate as taught in Chassaing et al. with the reasonable expectation of forming a Ni-Mo based catalyst layer capable of the HER portion of water splitting.
It has been held that a prima facie case of obviousness exists when an example disclosed in the prior art falls within the claimed range of the instant application (e.g.: the concentrations of Ni-precursor, Mo-precursor, and sodium citrate in the plating bath). See MPEP 2144.05(I): OVERLAPPING, APPROACHING, AND SIMILAR RANGES, AMOUNTS, AND PROPORTIONS
Regarding Claim 7, An et al. in view of Chassaing et al. discloses the method of Claim 6 wherein the obtaining of the plating solution, 0.20 M nickel precursor, 0.25 M sodium citrate, and 7.5 mM molybdenum precursor are dissolved in deionized water as per the formulation of electrolyte A listed in Table 1 of Chassaing et al. (pg. 839). It has been held that a prima facie case of obviousness exists when an example disclosed in the prior art falls within the claimed range of the instant application (e.g.: the concentrations of Ni-precursor, Mo-precursor, and sodium citrate in the plating bath). See MPEP 2144.05(I): OVERLAPPING, APPROACHING, AND SIMILAR RANGES, AMOUNTS, AND PROPORTIONS
8. Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over An et al. as applied to Claim 8 above, and further in view of Halim et al.
An et al. (“One-Step Controllable Synthesis of Catalytic Ni4Mo/MoOx/Cu Nanointerfaces for Highly Efficient Water Reduction,” Adv. Energy Mater. 2019, 9, article 1901454, pg. 1-10 – previously presented) is directed toward alkaline hydrogen evolution (pg. 1: abstract). Halim et al. (“Electrodeposition and Characterization of Nanocrystalline Ni-Mo Catalysts for Hydrogen Production,” J. Nanomat. 2012, Article ID 845673, 1-9 – previously presented) is directed toward catalysts for hydrogen production (pg. 1: title).
Regarding Claim 10, An et al. discloses the method of Claim 8, wherein the forming of the catalyst layer further comprises: stirring the plating solution prepared before performing the electroplating as per the experimental section of the supporting information. An et al. clearly indicates that the solution is stirred, but is silent on the stir rate to ensure effective mass transfer toward and away from the electrode. An et al. also is also silent on the temperature of the plating bath during the electroplating process to form Ni4Mo in copper foam. Stir rate and temperature are both essential application parameters that are manipulated to ensure the deposition of a NiMo alloy, but not specified in An et al, so one of ordinary skill in the art would investigate other references to appropriately choose said parameters.
Halim et al. discloses bath concentrations and current densities applied to the plating solution (pg. 2: Table 2) which are similar to those taught in An et al for the formation of a NiMo alloy capable of splitting water. Halim et al. specifies the stir rate of 350 ± 5 rpm and an application temperature of 25 ± 1℃. On page 8, Halim et al. indicated that the deposited NiMo alloys were HER catalysts (Discussion section).
It would be obvious to one of ordinary skill in the art to modify the application method of An et al. by using the stirring rate and deposition temperature disclosed in Halim et al. with the reasonable expectation for depositing an alloy of Ni-Mo which is effective for the HER in water splitting.
It has been held that a prima facie case of obviousness exists when an example disclosed in the prior art falls within the claimed range of the instant application (e.g.: stir rate and bath temperature of the plating bath). See MPEP 2144.05(I): OVERLAPPING, APPROACHING, AND SIMILAR RANGES, AMOUNTS, AND PROPORTIONS
Response to Arguments
9. Since the applicant has supplied amended drawings for Fig. 3F which makes the objections to the specification and the drawings moot. Therefore, the examiners withdraws the objection.
10. To rebut the prima facie case of obviousness pertaining to the order of addition of the nickel precursor, sodium citrate, and the sodium molybdate, the applicant has highlighted the two dissolution sequences listed below:
Ex. 1 (preferable): sequentially dissolving the nickel precursor, the sodium citrate, and the molybdenum precursor in the solvent in ¶57-58 of the specification (pg. 7-8)
Ex. 14: dissolution of the nickel precursor and the dissolution of the molybdenum precursor were firstly performed, and then sodium citrate dissolution was performed
The above conditions were used to evaluate the effect of the order of addition on the composition of the catalyst and/or the electrochemical performance of the resultant catalyst. Ex. 1 resulted in a composition of 41.7 wt.% nickel, 20.6 wt.% molybdenum, and 37.7 wt.% oxygen and Ex. 14 resulted in a catalyst composition of 39.0 wt.% nickel, 22.2 wt.% molybdenum, and 38.8 wt.% oxygen (pg. 14: Table 4). The composition is very similar despite the difference in the order of addition. However, there appears to be a minor improvement in the electrochemical behavior of the catalyst prepared by the addition sequence in Ex. 1 as compared to the procedure for Ex. 14 as support by FIG. 3D (as per the applicant’s response on pg. 2-3).
However, the comparison above is only for one set of concentrations, i.e.: 0.1 M nickel precursor, 0.2 M sodium citrate, and 2.5 mM molybdenum precursor. In the specification, the applicant indicates that the electrolyte component can be used in a broader range, i.e.: a nickel precursor concentration ranging from 0.05 M to 0.30 M, a citrate concentration ranging from 0.10 M to 0.60 M, and a molybdenum precursor concentration ranging from 1 mM to 10 mM. Given the single electrolyte bath concentration comparing the order of addition (i.e.: narrow range of electrolyte compositions), the scope of Claim 1 is not commensurate with the evidence presented by the applicant as the limitations of Claim 1 indicate that the order of addition, i.e., the Ni precursor, then sodium citrate, and lastly the Mo precursor works across any electrolyte composition comprising a nickel precursor, a molybdenum precursor, and (sodium) citrate.
11. An et al. which has a composition comparable to the instant application indicates that the order of addition is not important to the formation of a Ni-Mo-O hydrogen evolution
catalyst, thus providing contrary evidence to the importance of the order of addition as required by Claim 1 of the instant application. The support for the order of addition not being critical for performance is the scheme below from the supporting information of An et al.:
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The scheme suggests that a nickel-citrate complex is formed despite the order of addition disclosed by An et al (i.e.: Ni precursor, followed by Mo precursor, and lastly citrate). As indicated in the office action above, the electrolyte bath concentrations in An et al. were 0.32 M nickel precursor, 0.19 M citrate, and 27 mM molybdenum precursor. Electrodeposition from said bath resulted in an HER catalyst having the composition 39.84 wt.% nickel, 23.58 wt.% molybdenum, and 36.58 wt.% oxygen as measured by EDX (Figure S4 in the supporting information of An et al.). This composition is very similar to both Ex. 1 and Ex. 14 discloses by the instant application.
13. Bastug et al. ("1:1 Binary complexes of citric acid with some metal ions: stability and thermodynamic parameters,” Rev. Inorg. Chem. 2007, 274, 53-65) also provides support for the lack of criticality of the order of addition of Ni, citrate, and Mo in the electrolyte as required by Claim 1. Bastug et al. is directed toward nickel citrate complexes (pg. 53: abstract). On pg. 62, Bastug discloses the log Kf of nickel-citrate complexes at various temperatures (Table 3). When these are converted to Kf values, the results are 1.23 x 105 at 15 °C, 1.55 x 105 at 25 °C, and 1.95 x 105 at 35 °C. The large Kf values indicate that binding of citrate to nickel is very thermodynamically favored suggesting that in the presents of other species (i.e.: molybdate) nickel cations will preferentially bind to citrate. Moreover, the concentration of the Mo precursor in the instant application is at least 5x less than the concentration of the nickel precursor and at least 10x less than the concentration of the citrate in the electrolyte, which would further suppress Ni-Mo cluster formation in favor of Ni-citrate complexation.
Conclusion
14. The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Sun et al. ( "Induced co-deposition of NiMo, NiW and CoW Alloys with competing side reactions," ECS Meeting Abstracts 2012, MA 2012-02, 3404) is directed towards the electrodeposition of binary alloys (title).
15. 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