DETAILED ACTION
Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 1-20 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Regarding claim 1, the metes and bounds of the claim are unclear regarding the spatial configuration and physical structure of the claimed "pores." Specifically, the claim presents an alternative ("or") structure that creates an internal contradiction and ambiguity as to where the pores are located and what physical entity defines them. In the first alternative, the claim recites that the "solid matrix defines pores distributed throughout the solid matrix and comprises a precursor metal oxide and domains of another metal oxide distributed throughout the precursor metal oxide." This clearly establishes that the pores are within the solid matrix itself. However, the second alternative recites: "or wherein the solid matrix comprises the precursor metal oxide and nanoparticles of the another metal oxide distributed on a surface of the solid matrix." By utilizing the alternative conjunction "or", the second alternative completely omits the limitation that the solid matrix "defines pores distributed throughout”.
Because of this phrasing, it would be unclear to one of ordinary skill in the art whether:
the solid matrix itself is inherently porous in both alternatives, and the second alternative merely changes the location of the secondary metal oxide (from "distributed throughout" to "nanoparticles on the surface")
the second alternative describes a completely non-porous solid matrix, meaning pores are entirely absent from this embodiment, and whether
the pores in the second alternative are not in the solid matrix, but are instead interstitial pores formed in between the individual nanoparticles of the "another metal oxide" distributed on the surface.
Because the claim language permits multiple, mutually exclusive structural interpretations regarding the existence, location, and nature of the porosity (e.g., whether the matrix itself is porous or if pores exist interstitially between oxide domains/nanoparticles), the structural limitations of the claim are unclear.
Claims 2-20 are rejected by dependency.
Claim Rejections - 35 USC § 102
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless – (a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1-2, 4-5, 7-9, 12, and 19-20 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Xiang et. al. (Xiang et. al., In Situ Vertical Growth of Fe−Ni Layered Double-Hydroxide Arrays on Fe−Ni Alloy Foil: Interfacial Layer Enhanced Electrocatalyst with Small Overpotential for Oxygen Evolution Reaction. ACS Energy Lett. 3, 2357−2365. 2018.)
Regarding claim 1, Xiang et. al. teaches an electrocatalytic material (Xiang, FeNi LDH nanosheets on metal foils, Figs. 1-2; FeNi LDH arrays on an FeNi alloy substrate are efficient catalysts toward the oxygen evolution reaction (OER), abstract) comprising:
structurally modified nanosheets and a substrate (Xiang, FeNi LDH nanosheets grown vertically on various metal foil substrates such as Fe, Ni, and an FeNi alloy, pg. 2358, col. 1, para. 3; Fig. 2),
each structurally modified nanosheet extending from a surface of the substrate and having a solid matrix (FeNi LDH nanosheets form a solid matrix and vertically extend from the surface of the FeNi alloy foil substrate; Fig. 5e),
wherein the solid matrix defines pores distributed throughout the solid matrix (nanosheets were grown vertically on each substrate foil directly, forming a uniform and porous FeNi LDH layer, pg. 2358, col. 2, para. 2, lines 1-8; Fig. 5e) and comprises a precursor metal oxide and domains of another metal oxide distributed throughout the precursor metal oxide (the precursor oxide is NiO6 and FeO6 domains are distributed throughout the NiO6 matrix, see Fig. 5e below);
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Fig. 5e from Xiang et. al.
Regarding claim 2, Xiang et. al. teaches all features of claim 1 as described above. Xiang et. al. further teaches wherein the precursor metal oxide and the another metal oxide are different metal oxides (the precursor oxide is NiO6 and FeO6 is distributed throughout the NiO6 matrix, see Fig. 5e above).
Regarding claim 4, Xiang et. al. teaches all features of claim 1 as described above. Xiang et. al. further teaches wherein the precursor metal oxide and the another metal oxide are independently selected from the group consisting of Fe oxides, Co oxides, Ni oxides, and Mn oxides (the precursor oxide is NiO6 and FeO6 is distributed throughout the NiO6 matrix, see Fig. 5e above).
Regarding claim 5, Xiang et. al. teaches all features of claim 1 as described above. Xiang et. al. further teaches wherein the precursor metal oxide is a Ni oxide and the another metal oxide is selected from the group consisting of Fe oxides, Co oxides, Mn oxides, and combinations thereof (the precursor oxide is NiO6 and FeO6 is distributed throughout the NiO6 matrix, see Fig. 5e above).
Regarding claim 7, Xiang et. al. teaches all features of claim 1 as described above. Xiang et. al. further teaches wherein the structurally modified nanosheets extend perpendicularly away from the surface of the substrate (FeO6 is distributed throughout the NiO6 matrix which extends perpendicularly away from the surface of the planar substrate; see Fig. 5e) and are in contact with neighboring structurally modified nanosheets at their respective sides or ends.
Regarding the limitation, “the structurally modified nanosheets …are in contact with neighboring structurally modified nanosheets at their respective sides or ends,” while Xiang et. al may not explicitly use the word 'contact,' Xiang et. al discloses that the nanosheets were grown vertically on each substrate foil directly, forming a uniform and porous FeNi LDH layer (pg. 2358, col. 2, para. 2, lines 1-8). Xiang et. al further teaches performing cyclic voltammetry (CV) on the electrocatalytic material (CV curves of FeNi LDH for OER on different substrates in Fig. 4). Under the Broadest Reasonable Interpretation (BRI), 'contact' encompasses electrical contact. Because the nanosheets form a uniform and porous FeNi LDH layer and further successfully undergo CV testing, they must inherently maintain an electrical pathway and be in electrical contact at their respective sides or ends to pass current. Therefore, Xiang et. al inherently discloses this limitation.
Regarding claim 8, Xiang et. al. teaches all features of claim 1 as described above. Xiang et. al. further teaches wherein the structurally modified nanosheets have an average thickness of no greater than 50 nm (the FeNi LDH nanosheets on different foils have a thickness of approximately 15−25 nm, pg. 2358, col. 2, para. 2 lines 1-8).
Regarding claim 9, Xiang et. al. teaches all features of claim 1 as described above. Xiang et. al. further teaches wherein the structurally modified nanosheets are porous nanosheets wherein the solid matrix defines pores distributed throughout the solid matrix (nanosheets were grown vertically on each substrate foil directly, forming a uniform and porous FeNi LDH layer, pg. 2358, col. 2, para. 2, lines 1-8) and comprises the precursor metal oxide and domains of the another metal oxide distributed throughout the precursor metal oxide (the precursor oxide is NiO6 and FeO6 domains are distributed throughout the NiO6 matrix; see Fig. 5e).
Regarding claim 12, Xiang et. al. teaches all features of claim 9 as described above. Xiang et. al. further teaches wherein the solid matrix has outer surfaces which are free of any nanostructures (FeO6 is distributed throughout the NiO6 matrix and the outer surfaces of the NiO6 matrix are free of nanoparticles or any external nanostructures; see Fig. 5e).
Regarding claim 19, Xiang et. al. teaches an electrocatalytic system comprising nanosheets grown vertically on a substrate foil, forming a uniform and porous FeNi LDH layer (pg. 2358, col. 2, para. 2, lines 1-8; Fig. 5e) wherein the nanosheets comprise a precursor metal oxide and domains of another metal oxide distributed throughout the precursor metal oxide (the precursor oxide is NiO6 and FeO6 is distributed throughout the NiO6 matrix, see Fig. 5e).
Xiang et. al. does not explicitly recite the phrases "electrochemical cell," "counter electrode," or "power source"; however, Xiang et. al. explicitly does disclose an electrode and electrolyte (pg. 2361, Fig. 4e) and additionally performing Oxygen Evolution Reaction (OER) activities on the disclosed catalyst materials, including cyclic voltammetry (CV) curves, Tafel plots, Nyquist plots, and chronoamperometry experiments (pg. 2361, Fig. 4). Under MPEP §2112, a prior art reference anticipates a claim if the missing characteristic is inherent in the disclosure. In this case, the Examiner notes that electrochemical experiments involving OER electrocatalytic evaluations (specifically CV testing, Tafel analysis, and chronoamperometry at a specified voltage versus a Reversible Hydrogen Electrode (RHE); pg. 2361, Fig. 4), by necessity, inherently requires and utilizes an electrocatalytic system setup consisting of:
an electrochemical cell holding an electrolyte solution (implied by the interface of the electrode/electrolyte in the recited charge-transfer resistance Rct and the RHE reference standard),
a working electrode containing the electrocatalytic material,
a counter electrode to complete the electrical circuit required to measure the mass activity and current densities described, and
a power source (e.g., a potentiostat or electrochemical workstation) configured to apply the stated electric potential (e.g., 1.5 V vs. RHE) across the electrodes.
The Examiner further notes that the components are "configured to" perform their respective functions (e.g., contain an aqueous electrolyte, apply an electric potential); it is well established that apparatus claims are patentably distinguished by their structural features, not their intended function or configuration capabilities (see MPEP § 2111). Because the system of Xiang et. al. explicitly performs these exact functions to generate the OER data, CV curves, and chronoamperometry datasets, the prior art structure inherently possesses the structure and capacity to be "configured" exactly as claimed. Accordingly, all structural elements and functional configurations of claim 1 are inherently anticipated by Xiang et. al.
Regarding claim 20, the claim recites “a method of using the electrocatalytic system of claim 19, comprising applying the electric potential to oxidize water and produce O2.” As set forth in the rejection of claim 19 above, Xiang et. al. discloses an electrocatalytic system including an electrochemical cell configured to contain an aqueous electrolyte solution, an electrode comprising the material of claim 1, a counter electrode, and a power source configured to apply an electric potential across the electrodes. Xiang et. al. further inherently discloses applying the electric potential to oxidize water and produce O2.
Specifically, Xiang et. al. explicitly discloses that the first release of a proton from an adsorbed water molecule leaving an adsorbed -OH, was the rate-determining step of the oxygen evolution reaction (OER) process (pg. 2363, col. 1, para. 2, lines 34-44 through para. 3 lines 1-5). The oxygen evolution reaction (OER) is, by definition in the electrochemical arts, the chemical reaction in which water is oxidized to produce oxygen (O2). By explicitly disclosing the facilitation of the dissociation of the O–H bond of H2O and the promotion of the OER process within an identical electrocatalytic system, Xiang et. al. inherently operates by applying an electric potential to oxidize water and produce O2. Therefore, since Xiang et. al. utilizes an identical electrocatalytic system under conditions that promote the OER process, the system of Xiang et. al. inherently oxidizes water and produces O2 upon the application of an electric potential. Therefore, the method of claim 20 is anticipated by Xiang et. al.
Claims 1-2, 7, 13-14, and 16-20 are alternatively rejected under 35 U.S.C. 102(a)(1) as being anticipated by Hou et. al. (Hou et. al Branched WO3 Nanosheet Array with Layered C3N4 Heterojunctions and CoOx Nanoparticles as a Flexible Photoanode for Efficient Photoelectrochemical Water Oxidation. Adv. Mater. 26, 5043–5049. 2014.)
Regarding claim 1, Hou et. al. discloses a hybrid three-dimensionally branched heterojunction structure electrocatalyst material for photoelectrochemical water oxidation, comprising a tungsten wire mesh substrate supporting a WO₃ nanosheet array, a C₃N₄ nanosheet coating, and CoOₓ nanoparticles (pg. 5043, col. 2, para. 2; Scheme 1). The nanosheets were structurally modified to comprise CoOx nanoparticle on the outer surface of the nanosheets (CoOₓ nanoparticles were deposited on the WO3-NA/C3N4-NS to create the hybrid 3DB WO3-NA/C3N4-NS//CoOₓ; pg. 5043, col. 2, para. 2; Scheme 1). The nanosheets (WO3-NA/C3N4-NS) extend from the surface of the tungsten (W) mesh substrate and have a solid matrix (3DB WO3-NA/C3N4-NS//CoOₓ) that comprises a precursor metal oxide (WO3) and nanoparticles of another metal oxide (CoOₓ) distributed on the surface of the solid matrix, thereby forming a branched structure (Scheme 1).
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Scheme 1 from Hou et. al.
Regarding claim 2, Hou et. al. teaches all features of claim 1 as described above. Hou et. al. further teaches wherein the precursor metal oxide and the another metal oxide are different metal oxides (the precursor oxide is WO3 and the nanoparticles decorated on the outside of the 3DB WO3-NA/C3N4-NS matrix are CoOₓ, see Scheme 1).
Regarding claim 7, Hou et. al. teaches all features of claim 1 as described above. Hou et. al. further teaches wherein the structurally modified nanosheets extend perpendicularly away from the surface of the substrate and are in contact with neighboring structurally modified nanosheets at their respective sides or ends (the WO3-NA/C3N4-NS//CoOx nanosheets extend perpendicularly away from the surface of the W substrate and are in contact with other WO3-NA/C3N4-NS nanosheets; see Scheme 1).
Regarding claim 13, Hou et. al. discloses all features of claim 1 as described above, including a hybrid three-dimensionally branched heterojunction structure electrocatalyst material for photoelectrochemical water oxidation, comprising a tungsten wire mesh substrate supporting a WO₃ nanosheet array, a C₃N₄ nanosheet coating, and CoOₓ nanoparticles (pg. 5043, col. 2, para. 2; Scheme 1). The nanosheets were structurally modified to comprise CoOx nanoparticle on the outer surface of the nanosheets (CoOₓ nanoparticles were deposited on the WO3-NA/C3N4-NS to create the hybrid 3DB WO3-NA/C3N4-NS//CoOₓ; pg. 5043, col. 2, para. 2; Scheme 1). The nanosheets (WO3-NA/C3N4-NS) extend from the surface of the tungsten (W) mesh substrate and have a solid matrix (3DB WO3-NA/C3N4-NS//CoOₓ) that comprises a precursor metal oxide (WO3) and nanoparticles of another metal oxide (CoOₓ) distributed on the surface of the solid matrix, thereby forming the claimed branched nanosheet structure (Scheme 1).
Regarding claim 14, Hou et. al. teaches all features of claim 13 as described above, including branched nanosheets with surface-distributed cobalt oxide-based nanoparticles. Hou et. al. further teaches that the CoOx nanoparticles have a diameter of about 5 nm, which falls within the claimed range of no more than 50 nm (pg. 5045, col. 1, lines 1-2).
Regarding claim 16, Hou et. al. teaches all features of claim 13 as described above, including branched nanosheets with surface-distributed metal oxide nanoparticles. Specifically, Hou et. al. teaches a three-dimensionally branched (3DB) nanosheet array structure (3DB WO3 nanosheet array and the C3N4 nanosheets form a WO3-NA/C3N4-NS nanosheet structure; pg. 5043, col. 2, para. 2) wherein hybrid 3DB WO3-NA/C3N4-NS heterojunctions decorated with CoOx nanoparticles to form a solid matrix (3DB WO3-NA/C3N4-NS//CoOx) was utilized for efficient photoelectrochemical water oxidation (pg. 5043, col. 2, para. 2; see Scheme 1 below). Hou et. al. further teaches that the efficiency of such a 3DB heterojunction can be increased by integrating a nanoparticle electrocatalyst (CoOx), which provides active sites for water oxidation and also suppresses the formation of peroxo species, which would lower the over-potential, thereby prevent photocorrosion (pg. 5043, col. 2, para. 1, lines 7-14).
Although Hou et. al. further teaches that the nanosheets are interconnected to produce an open and porous microstructure (pg. 5044, col. 1, para. 1, lines 1-2; Fig. 1), the nanosheets themselves appear to be nonporous based on the FESEM images of the WO3-NA/C3N4-NS in Fig. 1d.
Regarding claim 17, Hou et. al. teaches all features of claim 13 as described above, including branched nanosheets with surface-distributed nanoparticles. Specifically, Hou et. al. teaches a three-dimensionally branched (3DB) nanosheet array structure (3DB WO3 nanosheet array and the C3N4 nanosheets form a WO3-NA/C3N4-NS nanosheet structure; pg. 5043, col. 2, para. 2) wherein hybrid 3DB WO3-NA/C3N4-NS heterojunctions decorated with CoOx nanoparticles to form a solid matrix (3DB WO3-NA/C3N4-NS//CoOx) was utilized for efficient photoelectrochemical water oxidation (pg. 5043, col. 2, para. 2; see Scheme 1). Hou et. al. further teaches that the efficiency of such a 3DB heterojunction can be increased by integrating a nanoparticle electrocatalyst (CoOx), which provides active sites for water oxidation and also suppresses the formation of peroxo species, which would lower the over-potential, thereby prevent photocorrosion (pg. 5043, col. 2, para. 1, lines 7-14).
Furthermore, Hou et. al. teaches wherein the solid matrix (3DB WO3-NA/C3N4-NS//CoOx) has outer surfaces which are free of any nanostructures except for the nanoparticles (Scheme 1 depicts no other nanostructures except CoOx nanoparticles on the outer surfaces of the WO3-NA/C3N4-NS nanosheets; TEM and HRTEM images of the WO3-NA/C3N4-NS//CoOx structure show no additional nanostructures other than the nanoparticles on the outer surface of the nanosheets, Fig. 2).
Regarding claim 18, Hou et. al. teaches all features of claim 17 as described above, including branched nanosheets with surface-distributed nanoparticles wherein the solid matrix has outer surfaces which are free of any nanostructures except for the nanoparticles.
Although Hou et. al. further teaches that the nanosheets are interconnected to produce an open and porous microstructure (pg. 5044, col. 1, para. 1, lines 1-2; Fig. 1), the nanosheets themselves appear to be nonporous based on the FESEM images of the WO3-NA/C3N4-NS in Fig. 1d.
Regarding claim 19, Hou et. al. teaches an electrocatalytic system comprising structurally modified nanosheets wherein the nanosheets comprise a precursor metal oxide and domains of another metal oxide distributed throughout the precursor metal oxide.
Hou et. al does not explicitly recite the phrases "electrochemical cell," "counter electrode," or "power source"; however, Hou et. al. explicitly does disclose an electrode and electrolyte (pg. 5046, col. 1, para. 1, lines 1-6) and additionally performing electrochemical impedance spectroscopy (EIS) measurements (EIS Nyquist plots in Fig. 3f). Under MPEP §2112, a prior art reference anticipates a claim if the missing characteristic is inherent in the disclosure. In this case, the Examiner notes that electrochemical experiments involving electrocatalytic evaluations of the material, by necessity, inherently requires and utilizes an electrocatalytic system setup consisting of:
an electrochemical cell holding an electrolyte solution (implied by the interface of the electrode/electrolyte),
a working electrode containing the electrocatalytic material,
a counter electrode to complete the electrical circuit required to measure the mass activity and current densities described, and
a power source (e.g., a potentiostat or electrochemical workstation) configured to apply the stated electric potential across the electrodes.
The Examiner further notes that the components are "configured to" perform their respective functions (e.g., contain an aqueous electrolyte, apply an electric potential); it is well established that apparatus claims are patentably distinguished by their structural features, not their intended function or configuration capabilities (see MPEP § 2111). Because the system of Hou et. al. explicitly performs these exact functions to generate the EIS datasets, the prior art structure inherently possesses the structure and capacity to be "configured" exactly as claimed. Accordingly, all structural elements and functional configurations of claim 1 are inherently anticipated by Hou et. al.
Regarding claim 20, the claim recites “a method of using the electrocatalytic system of claim 19, comprising applying the electric potential to oxidize water and produce O2.” As set forth in the rejection of claim 19 above, Hou et. al. discloses an electrocatalytic system including an electrochemical cell configured to contain an aqueous electrolyte solution, an electrode comprising the material of claim 1, a counter electrode, and a power source configured to apply an electric potential across the electrodes. Hou et. al. further inherently discloses applying the electric potential to oxidize water and produce O2.
Specifically, Hou et. al. explicitly discloses that holes in the heterojunction of the WO3-NA/C3N4-NS nanosheets are further transferred to the CoOx nanoparticles decorated on the outside of the nanosheets, which act both as active sites for the water oxidation and as suppressors of electron–hole recombination (pg. 5047, col. 1, para. 1, lines 15-20).
Water oxidation, in the electrochemical arts, involves the chemical reaction in which water is oxidized to produce oxygen (O2). By explicitly disclosing the facilitation of water oxidation using the claimed catalytic material, Hou et. al. inherently operates by applying an electric potential to oxidize water and produce O2. Therefore, the system of Hou et. al. inherently oxidizes water and produces O2 upon the application of an electric potential.
Claim Rejections - 35 USC § 103
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.
Claims 3, 6, 11, and 13-15 are rejected under 35 U.S.C. 103 as being unpatentable over Xiang et. al. as applied to claim 1 above, and further in view of Morales (Morales et. al., Trimetallic Mn-Fe-Ni Oxide Nanoparticles Supported on Multi-Walled Carbon Nanotubes as High-Performance Bifunctional ORR/OER Electrocatalyst in Alkaline Media. Adv. Funct. Mater, 30, 1905992. (2020)).
Regarding claim 3, Xiang et. al. teaches all features of claim 1 as described above, including nanosheets grown vertically on a substrate foil, forming a uniform and porous FeNi LDH layer (pg. 2358, col. 2, para. 2, lines 1-8; Fig. 5e) wherein the nanosheets comprise a precursor metal oxide and domains of another metal oxide distributed throughout the precursor metal oxide (the precursor oxide is NiO6 and FeO6 is distributed throughout the NiO6 matrix, see Fig. 5e). However, Xiang et. al. does not expressly teach wherein the solid matrix comprises three or more different metal oxides.
Morales teaches a transition metal oxide electrocatalyst for renewable energy conversion technologies such as rechargeable metal-air batteries and reversible electrolyzer systems, stating that discovering precious metal-free electrocatalysts with high activity and stability toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) remains a primary challenge (abstract). To address this challenge, Morales teaches that a highly active OER catalyst comprising a bimetallic oxide matrix Fe0.3Ni0.7Ox can be substantially activated into a highly active, bifunctional catalyst by means of additional incorporation of a third metal oxide, MnOx (pg. 2, col. 1, para. 3; pg. 2, col. 2, para. 2, lines 8-18), and that the resulting carbon nanotube-supported trimetallic Mn-Fe-Ni oxide catalyst system achieves remarkable bifunctional ORR/OER activity (pg. 8, col. 2, lines 4-6) and notably low ORR and OER overpotentials (pg. 9, col. 2, “Conclusion” section, lines 9-12) for improved electrocatalytic performance.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the electrocatalytic material of Xiang et al. by incorporating a third metal oxide (such as the MnOx taught by Morales) into the Fe-Ni matrix of Xiang et al. to form a trimetallic oxide matrix containing three different metal oxides. A POSITA would have been motivated to make this compositional modification because Morales demonstrates that adding a third transition metal oxide MnOx to an existing nickel-iron oxide matrix significantly boosts catalytic activation, reduces ORR/OER overpotentials, and improves electrocatalytic performance.
Regarding claim 6, Xiang et. al. teaches all features of claim 1 as described above, including nanosheets grown vertically on a substrate foil, forming a uniform and porous FeNi LDH layer (pg. 2358, col. 2, para. 2, lines 1-8; Fig. 5e) wherein the nanosheets comprise a precursor metal oxide and domains of another metal oxide distributed throughout the precursor metal oxide (the precursor oxide is NiO6 and FeO6 domains are distributed throughout the NiO6 matrix, see Fig. 5e). However, Xiang et. al. does not expressly teach wherein the precursor metal oxide is a Ni oxide and the another metal oxide is a combination of Fe oxides and Mn oxides.
Morales teaches a transition metal oxide electrocatalyst for renewable energy conversion technologies such as rechargeable metal-air batteries and reversible electrolyzer systems, stating that discovering precious metal-free electrocatalysts with high activity and stability toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) remains a primary challenge (abstract). To address this challenge, Morales teaches that a highly active OER catalyst comprising a bimetallic oxide matrix Fe0.3Ni0.7Ox can be substantially activated into a highly active, bifunctional catalyst by means of additional incorporation of a third metal oxide, MnOx (pg. 2, col. 1, para. 3; pg. 2, col. 2, para. 2, lines 8-18), and that the resulting carbon nanotube-supported trimetallic Mn-Fe-Ni oxide catalyst system achieves remarkable bifunctional ORR/OER activity (pg. 8, col. 2, lines 4-6) and notably low ORR and OER overpotentials (pg. 9, col. 2, “Conclusion” section, lines 9-12) for improved electrocatalytic performance.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the electrocatalytic material of Xiang et al. by incorporating a third metal oxide (such as the MnOx taught by Morales) into the Fe-Ni matrix of Xiang et al. to form a trimetallic oxide matrix containing three different metal oxides such that the precursor oxide is a Ni oxide and the another metal oxide is a combination of Fe oxides and Mn oxides. A POSITA would have been motivated to make this compositional modification because Morales demonstrates that adding a third transition metal oxide MnOx to an existing nickel-iron oxide matrix significantly boosts catalytic activation, reduces ORR/OER overpotentials, and improves electrocatalytic performance.
Regarding claim 11, Xiang et. al. teaches all features of claim 9 as described above, including nanosheets grown vertically on a substrate foil, forming a uniform and porous FeNi LDH layer (pg. 2358, col. 2, para. 2, lines 1-8; Fig. 5e) wherein the nanosheets comprise a precursor metal oxide and domains of another metal oxide distributed throughout the precursor metal oxide (the precursor oxide is NiO6 and FeO6 domains are distributed throughout the NiO6 matrix, see Fig. 5e). Xiang et. al. does not expressly teach wherein the precursor metal oxide is Ni oxide and the domains comprise both Fe oxide domains and Mn oxide domains.
Morales teaches a transition metal oxide electrocatalyst for renewable energy conversion technologies such as rechargeable metal-air batteries and reversible electrolyzer systems, stating that discovering precious metal-free electrocatalysts with high activity and stability toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) remains a primary challenge (abstract). To address this challenge, Morales teaches that a highly active OER catalyst comprising a bimetallic oxide matrix Fe0.3Ni0.7Ox can be substantially activated into a highly active, bifunctional catalyst by means of additional incorporation of a third metal oxide, MnOx (pg. 2, col. 1, para. 3; pg. 2, col. 2, para. 2, lines 8-18), and that the resulting carbon nanotube-supported trimetallic Mn-Fe-Ni oxide catalyst system achieves remarkable bifunctional ORR/OER activity (pg. 8, col. 2, lines 4-6) and notably low ORR and OER overpotentials (pg. 9, col. 2, “Conclusion” section, lines 9-12) for improved electrocatalytic performance.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the electrocatalytic material of Xiang et al. by incorporating a third metal oxide (such as the MnOx taught by Morales) into the Fe-Ni matrix of Xiang et al. such that the domains distributed within the Ni oxide matrix comprise both Fe oxide and Mn oxide domains. A POSITA would have been motivated to make this compositional modification because Morales demonstrates that adding a third transition metal oxide MnOx to an existing nickel-iron oxide matrix significantly boosts catalytic activation, reduces ORR/OER overpotentials, and improves electrocatalytic performance. Such a modification represents the predictable combination of prior art elements according to known methods to achieve the predictable result of enhanced electrocatalytic performance.
Regarding claim 13, Xiang et. al. teaches all features of claim 1 as described above, including nanosheets grown vertically on a substrate foil, forming a uniform and porous FeNi LDH layer (pg. 2358, col. 2, para. 2, lines 1-8; Fig. 5e) wherein the nanosheets comprise a precursor metal oxide and domains of another metal oxide distributed throughout the precursor metal oxide (the precursor oxide is NiO6 and FeO6 domains are distributed throughout the NiO6 matrix, see Fig. 5e). Xiang et. al. does not expressly teach wherein the structurally modified nanosheets are branched nanosheets wherein the solid matrix comprises the precursor metal oxide and nanoparticles of another metal oxide distributed on the surface of the solid matrix.
Morales teaches a transition metal oxide electrocatalyst for renewable energy conversion technologies such as rechargeable metal-air batteries and reversible electrolyzer systems, stating that discovering precious metal-free electrocatalysts with high activity and stability toward both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) remains a primary challenge (abstract). To address this challenge, Morales teaches that a highly active OER catalyst comprising a bimetallic oxide matrix Fe0.3Ni0.7Ox can be substantially activated into a highly active, bifunctional catalyst by means of additional incorporation of a third metal oxide, MnOx (pg. 2, col. 1, para. 3; pg. 2, col. 2, para. 2, lines 8-18), and that the resulting carbon nanotube-supported trimetallic Mn-Fe-Ni oxide catalyst system achieves remarkable bifunctional ORR/OER activity (pg. 8, col. 2, lines 4-6) and notably low ORR and OER overpotentials (pg. 9, col. 2, “Conclusion” section, lines 9-12) for improved electrocatalytic performance.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the Fe-Ni nanosheets of Xiang et al. by incorporating an additional transition metal oxide (such as the MnOx taught by Morales) on the surface of Xiang et. al.’s solid matrix to form branched nanosheets with surface-distributed nanoparticles (nanoparticles; pg. 2, col. 2, para. 1, lines 5-10). A POSITA would have been motivated to make this modification because Morales demonstrates that (1) adding a third transition metal oxide MnOx to an existing nickel-iron oxide matrix significantly boosts catalytic activation, reduces ORR/OER overpotentials, and improves electrocatalytic performance, and (2) Morales further discloses that the electrical resistances inherent to metal oxides are overcome by connecting MOX-nanoparticles with MWCNTs-Ox, which not only provides high electrical conductivity but also a high degree of nanoparticle dispersion and, thus, a high surface area (nanoparticles; pg. 2, col. 2, para. 1, lines 5-10).
Regarding claim 14, modified Xiang et. al. teaches all features of claim 13 as described above, including branched nanosheets with surface-distributed nanoparticles (pg. 2, col. 2, para. 1, lines 5-10). Modified Xiang et. al. does not expressly teach wherein the nanoparticles have an average diameter of no more than 50 nm.
Morales further discloses that the size of the nanoparticles deposited on the outer walls of MWCNTs-Ox are all less than 50 nm, which overlaps with the claimed range (see Table S5 below; pg. 5, col. 1, para. 1, lines 4-13).
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Table S5 from Morales
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Morales, because overlapping ranges have been held to establish prima facie obviousness.
Regarding claim 15, modified Xiang et. al. (Xiang et. al. as modified by Morales) teaches all features of claim 13 as described above, including branched nanosheets with surface-distributed nanoparticles (Morales, pg. 2, col. 2, para. 1, lines 5-10). Claim 15 further requires the specific oxide materials such that the precursor metal oxide is a Ni oxide, and the nanoparticles comprise Fe oxide and Mn oxide nanoparticles. Xiang et. al. in view of Morales teaches that the precursor metal oxide is a Ni oxide and the nanoparticles comprise Fe oxide nanoparticles. Furthermore, Morales teaches incorporating an additional transition metal oxide, specifically manganese oxide (MnOx) (Morales, pg. 2, col. 1, para. 3; pg. 2, col. 2, para. 2, lines 8-18).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the surface-distributed nanoparticles of Xiang et al. by incorporating an additional transition metal oxide (such as the MnOx taught by Morales) on the surface of Xiang et. al.’s solid matrix to form branched nanosheets with surface-distributed Fe and Mn oxide nanoparticles. A POSITA would have been motivated to make this modification because Morales demonstrates that (1) adding a third transition metal oxide MnOx to an existing nickel-iron oxide matrix significantly boosts catalytic activation, reduces ORR/OER overpotentials, and improves electrocatalytic performance (as discussed in the rejection of claim 13 above), and (2) Morales further discloses that the electrical resistances inherent to metal oxides are overcome by connecting MOX-nanoparticles with MWCNTs-Ox, which not only provides high electrical conductivity but also a high degree of nanoparticle dispersion and, thus, a high surface area (Morales, pg. 2, col. 2, para. 1, lines 5-10).
Claims 16-18 are rejected under 35 U.S.C. 103 as being unpatentable over Xiang et. al. and Morales as applied to claim 13 above, and further in view of Hou et. al. (Hou et. al Branched WO3 Nanosheet Array with Layered C3N4 Heterojunctions and CoOx Nanoparticles as a Flexible Photoanode for Efficient Photoelectrochemical Water Oxidation. Adv. Mater. 26, 5043–5049. 2014.).
Regarding claim 16, modified Xiang et. al. (as modified by Morales in claim 13) teaches all features of claim 13 as described above, including branched nanosheets with surface-distributed nanoparticles (Morales, pg. 2, col. 2, para. 1, lines 5-10). However, modified Xiang et. al. does not expressly teach wherein the branched nanosheets are not porous.
Hou teaches a three-dimensionally branched (3DB) nanosheet array structure (3DB WO3 nanosheet array and the C3N4 nanosheets form a WO3-NA/C3N4-NS nanosheet structure; pg. 5043, col. 2, para. 2) wherein hybrid 3DB WO3-NA/C3N4-NS heterojunctions decorated with CoOx nanoparticles to form a solid matrix (3DB WO3-NA/C3N4-NS//CoOx) was utilized for efficient photoelectrochemical water oxidation (pg. 5043, col. 2, para. 2; see Scheme 1 below).
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Scheme 1 from Hou et. al.
Hou et. al. further teaches that the efficiency of such a 3DB heterojunction can be increased by integrating a nanoparticle electrocatalyst (CoOx), which provides active sites for water oxidation and also suppresses the formation of peroxo species, which would lower the over-potential, thereby prevent photocorrosion (pg. 5043, col. 2, para. 1, lines 7-14). Although Hou et. al. teaches that the nanosheets are interconnected to produce an open and porous microstructure (pg. 5044, col. 1, para. 1, lines 1-2; Fig. 1), the nanosheets themselves appear to be nonporous based on the FESEM images of the WO3-NA/C3N4-NS in Fig. 1d.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the nanosheets of Xiang et. al. to be non-porous, as demonstrated by Hou et. al. in order to achieve the known benefits of the branched nanosheet configuration such as lowering the over-potential, with reasonable expectation of success in creating an electrocatalytic material with efficient water oxidation properties.
Regarding claim 17, modified Xiang et. al. (as modified by Morales) teaches all features of claim 13 as described above, including branched nanosheets with surface-distributed nanoparticles (Morales, pg. 2, col. 2, para. 1, lines 5-10), but does not expressly teach wherein the solid matrix has outer surfaces which are free of any nanostructures except for the nanoparticles.
Hou et. al. teaches a three-dimensionally branched (3DB) nanosheet array structure (3DB WO3 nanosheet array and the C3N4 nanosheets form a WO3-NA/C3N4-NS nanosheet structure; pg. 5043, col. 2, para. 2) wherein hybrid 3DB WO3-NA/C3N4-NS heterojunctions decorated with CoOx nanoparticles to form a solid matrix (3DB WO3-NA/C3N4-NS//CoOx) was utilized for efficient photoelectrochemical water oxidation (pg. 5043, col. 2, para. 2; see Scheme 1). Hou et. al. further teaches that the efficiency of such a 3DB heterojunction can be increased by integrating a nanoparticle electrocatalyst (CoOx), which provides active sites for water oxidation and also suppresses the formation of peroxo species, which would lower the over-potential, thereby prevent photocorrosion (pg. 5043, col. 2, para. 1, lines 7-14). Hou et. al. further teaches wherein the solid matrix (3DB WO3-NA/C3N4-NS//CoOx) has outer surfaces which are free of any nanostructures except for the nanoparticles (Scheme 1 depicts no other nanostructures except CoOx nanoparticles on the outer surfaces of the nanosheets which are the WO3-NA/C3N4-NS; TEM and HRTEM images of the WO3-NA/C3N4-NS//CoOx structure show no additional nanostructures other than the nanoparticles on the outer surface of the nanosheets, Fig. 2).
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the nanosheets of Xiang et. al. to be free of any nanostructures except for the nanoparticles, as demonstrated by Hou et. al., in order to achieve the known benefits of the branched nanosheet configuration such as lowering the over-potential, with reasonable expectation of success in creating an electrocatalytic material with efficient water oxidation properties.
Regarding claim 18, modified Xiang et. al. (as further modified by Hou in claim 17) teaches all features of claim 17 as described above, including branched nanosheets with surface-distributed nanoparticles wherein the solid matrix has outer surfaces which are free of any nanostructures except for the nanoparticles. However, modified Xiang et. al. does not expressly teach wherein the branched nanosheets are not porous.
Hou et. al. further teaches a three-dimensionally branched (3DB) nanosheet array structure (3DB WO3 nanosheet array and the C3N4 nanosheets form a WO3-NA/C3N4-NS nanosheet structure; pg. 5043, col. 2, para. 2) wherein hybrid 3DB WO3-NA/C3N4-NS heterojunctions decorated with CoOx nanoparticles to form a solid matrix (3DB WO3-NA/C3N4-NS//CoOx) was utilized for efficient photoelectrochemical water oxidation (pg. 5043, col. 2, para. 2; see Scheme 1). Hou et. al. further teaches that the efficiency of such a 3DB heterojunction can be increased by integrating a nanoparticle electrocatalyst (CoOx), which provides active sites for water oxidation and also suppresses the formation of peroxo species, which would lower the over-potential, thereby prevent photocorrosion (pg. 5043, col. 2, para. 1, lines 7-14). Although Hou et. al. teaches that the nanosheets are interconnected to produce an open and porous microstructure (pg. 5044, col. 1, para. 1, lines 1-2; Fig. 1), the nanosheets themselves appear to be nonporous based on the FESEM images of the WO3-NA/C3N4-NS in Fig. 1d.
Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to modify the nanosheets of Xiang et. al. to be non-porous, as demonstrated by Hou et. al., in order to achieve the known benefits of the branched nanosheet configuration such as lowering the over-potential, with reasonable expectation of success in creating an electrocatalytic material with efficient water oxidation properties.
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Xiang et. al. as applied to claim 1 above, and further in view of Luz (WO2019191034A1; US20210008529A1 used for purposes of translation).
Regarding claim 10, Xiang et. al. teaches all features of claim 9 as described above. Xiang et. al. does not expressly teach wherein the pores have an average diameter of no more than 10 nm and the domains have an average diameter of no more than 50 nm.
Luz teaches a strategy for preparing highly active, nano-sized catalytic materials utilizing controlled thermal transformation of metal-organic framework (MOF) nanocrystals with multi-metallic metal oxides ([0056]). Luz further discloses that the precursor consists of nano-sized MOF domains with an average diameter range of 5–50 nm ([0006]), which overlaps with the claimed range of no more than 50 nm. Furthermore, Luz teaches confining these resulting supported nanocatalysts inside a mesoporous material scaffold, wherein the mesoporous material is explicitly defined as containing pores with a diameter range of 2–50 nm ([0070]), which overlaps with the claimed range of no more than 10 nm.
When the prior art discloses a general range that overlaps or routinely encompasses the claimed range, a prima facie case of obviousness is established (see MPEP §2144.05). Therefore, it would have been obvious to someone of ordinary skill in the art before the effective filing date of the claimed invention to have selected from the overlapping portion of the ranges taught by Luz, because overlapping ranges have been held to establish prima facie obviousness.
Conclusion
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/A.R.O./Examiner, Art Unit 1789
/MARLA D MCCONNELL/Supervisory Patent Examiner, Art Unit 1789
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