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 .
Claims 1-20 are pending and under consideration for this Office Action.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim(s) 1-6, 10-15, and 17-19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Klose et al (“Membrane Interlayer with Pt Recombination Particles for Reduction of the Anodic Hydrogen Content in PEM Water Electrolysis”, Journal of The Electrochemical Society, 165, 16, F1271-F1277, 2018) in view of
Lokesh et al (“Advanced Two-Dimensional Materials for Green Hydrogen Generation: Strategies toward Corrosion Resistance Seawater Electrolysis─Review and Future Perspectives”, Energy & Fuels, Vol 36, Issue 22, October 2022, pages 13417-13450),
Rijnaarts et al (“Layer-by-Layer Self-Assembly of Composite Polyelectrolyte–Nafion Membranes for Direct Methanol Fuel Cell”, Advanced Materials, Volume 18, Issue 8, April, 2006, Pages 1068-1072), and
Nelson et al (US 20080179188 A1).
Chemours (“Nafion NR211 and NR212 Ion Exchange Materials) and Sigma-Aldrich (“Nafion™ perfluorinated membrane”) cited as evidentiary references for claims 2-4 and 18-19.
Claim 1: Klose discloses a proton exchange membrane (see e.g. abstract) comprising:
a reinforced membrane having a first surface and a second surface (see e.g. “NR-212” on Fig 2), the reinforced membrane having a thickness of less than 100 μm (51 μm, see e.g. “NR-212” on Fig 2); and
a continuous nonporous hydrogen recombination catalyst coating layer (Pt with Nafion, see e.g. page F1273, col 1, paragraph “Pt interlayer”) having a first surface and a second surface (see e.g. “Interlayer” on Fig 2), the first surface of the continuous hydrogen recombination catalyst coating layer on the first surface of the reinforced membrane (see e.g. “Interlayer” on Fig 2), the, the continuous nonporous hydrogen recombination catalyst coating layer comprising a mixture of a hydrogen recombination catalyst and a proton conducting ionomer (Pt with Nafion, see e.g. page F1273, col 1, paragraph “Pt interlayer”).
Klose does not explicitly teach a continuous nonporous cross-linked polyelectrolyte multilayer coating on the second surface of the continuous nonporous hydrogen recombination catalyst coating layer, the nonporous cross-linked polyelectrolyte multilayer coating comprising alternating layers of a polycation polymer and a polyanion polymer, and wherein the polycation polymer layer is in contact with the continuous nonporous hydrogen recombination catalyst coating layer.
Klose teaches that the membrane is used for water electrolysis (see e.g. abstract). Lokesh teaches that “Green hydrogen generation through seawater electrolysis has been an emergent technology that can play a prominent role in replacing conventional energy sources. Electrolysis of seawater using renewable sources such as solar, wind, and geothermal generates green hydrogen which has almost negligible harmful byproducts. Different ions present in seawater such as chlorides and sulfates impose serious corrosion problems during the electrolysis process as chloride ions penetrate the metal electrode surface and oxidize it and also liberate chlorine gas at the anode” (see e.g. abstract). Rijnaarts discloses a membrane having a first polyelectrolyte multilayer coating coated on a first surface of the ion-exchange membrane layer and a second polyelectrolyte multilayer coating coated on a second surface of the ion-exchange membrane layer (see e.g. Fig 5, “recipe 2”). These layers give the membranes valent-based selectivity (see e.g. page 516, col 1, paragraph starting with “In this study”) including blocking sulfates. Nelson teaches that these membranes (see e.g. abstract, Fig 4) have a broad application, including electrolysis (see e.g. [0163]). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to include polyelectrolyte multilayer coatings on either side of the membrane of Klose as taught in Rijnaarts to block the movement of unwanted ions when using non-pure feedstocks, such as seawater. Furthermore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention that one of the first polyelectrolyte multilayers (arbitrarily referred to as the “first”) would be coated on the catalyst layer based on the disclosure of Klose having the catalyst directly applied to the membrane.
Claim 2: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the reinforced membrane comprises a single layer membrane comprising a first reinforcement material and a first proton conducting ionomer (Klose - the layer is NR-212. As evidenced by Chemours, NR-212 comprises PTFE, a first reinforcement material, and PFSA, a first proton conducting ionomer).
Claim 3: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the first proton conducting ionomer comprises a perfluorosulfonic acid (PFSA) polymer selected from copolymer of tetrafluoroethylene and perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (NR-212, as evidenced by Sigma-Aldrich).
Claim 4: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the first reinforcement material comprises polytetrafluoroethylene (PTFE) (As evidenced by Chemours).
Claim 5: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the thickness of the reinforced membrane is in a range of 10 to 90 μm (51 μm, see e.g. Klose - “NR-212” on Fig 2).
Claim 6: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the hydrogen recombination catalyst comprises Pt (see e.g. Klose - page F1273, col 1, paragraph “Pt interlayer”).
Claim 10: Klose in view of Lokesh, Rijnaarts, and Nelson does not explicitly teach a second continuous nonporous polyelectrolyte multilayer coating on the second surface of the reinforced membrane. Rijnaarts teaches that the polyelectrolyte multilayer coating gives membranes valent-based selectivity (see e.g. page 516, col 1, paragraph starting with “In this study”) including blocking sulfates. Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to include polyelectrolyte multilayer coatings on either side of the membrane as taught in Rijnaarts to block the movement of unwanted ions when using non-pure feedstocks, such as seawater.
Claim 11: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the continuous nonporous cross-linked polyelectrolyte multilayer coating comprises at least two sets of alternating layers of the polycation polymer and the polyanion polymer (see e.g. Rijnaarts – alternating layers on Fig 5).
Claim 12: Klose in view of Lokesh, Rijnaarts, and Nelson teaches a ratio of the proton conducting ionomer to the hydrogen recombination catalyst greater than 500:1 (see e.g. page F1272, col 1, paragraph starting with “In order to prepare”). However, a person having ordinary skill in the art before the effective filing date of the instant invention would understand that the ratio of the proton conducting ionomer to the hydrogen recombination catalyst would affect the activity of said layer and that the example of Klose was just a single example that did not fully explore the range of Pt loading. Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to adjust the ratio of the proton conducting ionomer to the hydrogen recombination catalyst to get the desired recombination activity.
Claim 13: Klose discloses a catalyst-coated membrane (see e.g. Figure 2) comprising:
a proton exchange membrane comprising (see e.g. abstract);
a reinforced membrane having a first surface and a second surface (see e.g. “NR-212” on Fig 2), the reinforced membrane having a thickness of less than 100 μm (51 μm, see e.g. “NR-212” on Fig 2); and
a continuous nonporous hydrogen recombination catalyst coating layer ( top layer including Pt with Nafion, see e.g. page F1273, col 1, paragraph “Pt interlayer”) having a first surface and a second surface (see e.g. “Interlayer” and “N115” on Fig 2), the first surface of the continuous hydrogen recombination catalyst coating layer on the first surface of the reinforced membrane (see e.g. “Interlayer” on Fig 2), the, the continuous nonporous hydrogen recombination catalyst coating layer comprising a mixture of a hydrogen recombination catalyst and a proton conducting ionomer (Pt with Nafion, see e.g. page F1273, col 1, paragraph “Pt interlayer”).
an anode on a second surface of the coating (“Anode”, see e.g. Figure 2); and
a cathode on the second surface of the reinforced membrane (“Cathode”, see e.g. Figure 2).
Klose does not explicitly teach a continuous nonporous cross-linked polyelectrolyte multilayer coating on the second surface of the continuous nonporous hydrogen recombination catalyst coating layer, the nonporous cross-linked polyelectrolyte multilayer coating comprising alternating layers of a polycation polymer and a polyanion polymer, and wherein the polycation polymer layer is in contact with the continuous nonporous hydrogen recombination catalyst coating layer.
Klose teaches that the membrane is used for water electrolysis (see e.g. abstract). Lokesh teaches that “Green hydrogen generation through seawater electrolysis has been an emergent technology that can play a prominent role in replacing conventional energy sources. Electrolysis of seawater using renewable sources such as solar, wind, and geothermal generates green hydrogen which has almost negligible harmful byproducts. Different ions present in seawater such as chlorides and sulfates impose serious corrosion problems during the electrolysis process as chloride ions penetrate the metal electrode surface and oxidize it and also liberate chlorine gas at the anode” (see e.g. abstract). Rijnaarts discloses a membrane having a first polyelectrolyte multilayer coating coated on a first surface of the ion-exchange membrane layer and a second polyelectrolyte multilayer coating coated on a second surface of the ion-exchange membrane layer (see e.g. Fig 5, “recipe 2”). These layers give the membranes valent-based selectivity (see e.g. page 516, col 1, paragraph starting with “In this study”) including blocking sulfates. Nelson teaches that these membranes (see e.g. abstract, Fig 4) have a broad application, including electrolysis (see e.g. [0163]). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to include polyelectrolyte multilayer coatings on either side of the membrane of Klose as taught in Rijnaarts to block the movement of unwanted ions when using non-pure feedstocks, such as seawater. Furthermore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention that one of the first polyelectrolyte multilayers (arbitrarily referred to as the “first”) would be coated on the catalyst layer based on the disclosure of Klose having the catalyst directly applied to the membrane.
Claim 14: Klose discloses a method of preparing proton exchange membrane (see e.g. abstract; page F1272, col 1) comprising:
applying a continuous nonporous hydrogen recombination catalyst coating layer (Pt with Nafion, see e.g. page F1273, col 1, paragraph “Pt interlayer”) directly on a first surface of a reinforced membrane (see e.g. “NR-212” on Fig 2), the continuous nonporous hydrogen recombination catalyst coating layer comprising a mixture of a recombination catalyst and a proton conducting ionomer (Pt with Nafion and N115, see e.g. page F1273, col 1, paragraph “Pt interlayer” and Fig 2), the reinforced membrane having a thickness of less than or equal to 100 μm (51 μm, see e.g. “NR-212” on Fig 2).
Klose does not explicitly teach applying a continuous nonporous cross-linked polyelectrolyte multilayer coating directly on a surface of the continuous nonporous hydrogen recombination catalyst coating layer, the continuous nonporous cross-linked polyelectrolyte multilayer coating comprising alternating layers of a polycation polymer and a polyanion polymer, wherein the polycation polymer layer is in contact with the continuous nonporous hydrogen recombination catalyst coating layer.
Klose teaches that the membrane is used for water electrolysis (see e.g. abstract). Lokesh teaches that “Green hydrogen generation through seawater electrolysis has been an emergent technology that can play a prominent role in replacing conventional energy sources. Electrolysis of seawater using renewable sources such as solar, wind, and geothermal generates green hydrogen which has almost negligible harmful byproducts. Different ions present in seawater such as chlorides and sulfates impose serious corrosion problems during the electrolysis process as chloride ions penetrate the metal electrode surface and oxidize it and also liberate chlorine gas at the anode” (see e.g. abstract). Rijnaarts discloses a membrane having a first polyelectrolyte multilayer coating coated on a first surface of the ion-exchange membrane layer and a second polyelectrolyte multilayer coating coated on a second surface of the ion-exchange membrane layer (see e.g. Fig 5, “recipe 2”). These layers give the membranes valent-based selectivity (see e.g. page 516, col 1, paragraph starting with “In this study”) including blocking sulfates. Nelson teaches that these membranes (see e.g. abstract, Fig 4) have a broad application, including electrolysis (see e.g. [0163]). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to modify the method to apply polyelectrolyte multilayer coatings on of the membrane of Klose as taught in Rijnaarts to block the movement of unwanted ions when using non-pure feedstocks, such as seawater. Furthermore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention that one of the first polyelectrolyte multilayers (arbitrarily referred to as the “first”) would be coated on the catalyst layer based on the disclosure of Klose having the catalyst directly applied to the membrane.
Claim 15: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the reinforced membrane comprises a single layer membrane comprising a first reinforcement material and a first proton conducting ionomer (Klose - the layer is NR-212. As evidenced by Chemours, NR-212 comprises PTFE, a first reinforcement material, and PFSA, a first proton conducting ionomer).
Claim 17: Klose in view of Lokesh, Rijnaarts, and Nelson teaches applying an anode directly on a second surface of the continuous nonporous cross-linked polyelectrolyte multilayer coating (see e.g. “Anode” on Fig 2); and applying a cathode directly to a second surface of the reinforced membrane (see e.g. “Cathode” on Fig 2).
Claim 18: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the first proton conducting ionomer comprises a perfluorosulfonic acid (PFSA) polymer selected from copolymer of tetrafluoroethylene and perfluoro-3,6-dioxa-4-methyl-7-octene-sulfonic acid (NR-212, as evidenced by Sigma-Aldrich).
Claim 19: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the first reinforcement material comprises polytetrafluoroethylene (PTFE) (As evidenced by Chemours).
Claim(s) 7 and 20 is/are rejected under 35 U.S.C. 103 as being unpatentable over Klose in view of Lokesh, Rijnaarts, and Nelson as applied to claims 1 and 14 above, and in further view of Sigma-Aldrich (“Nafion™ perfluorinated resin solution “, 2022, referred to as Sigma1 herein) and Sigma-Aldrich (“Aquivion® D98-25BS”, 2022, referred to as Sigma2 herein).
Claim 7: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the proton conducting ionomer in the continuous nonporous hydrogen recombination catalyst coating layer comprises a perfluorosulfonic acid (PFSA) polymer (Nafion, see e.g. Klose - page F1272, col 1, paragraph starting with “In order”). However, Klose does not explicitly disclose using a form of Nafion claimed in claim 7. Klose teaches using D2020 see e.g. Klose - page F1272, col 1, paragraph starting with “In order”). The product page for D2020 says it has been discontinued and recommends using D98-25BS (see e.g. Sigma1). D98-25BS comprises a perfluorosulfonic acid (PFSA) polymer selected from copolymer of tetrafluoroethylene and perfluoro-3-oxa-4-pentene-sulfonic acid (see e.g. Sigma2). MPEP § 2144.07 states ‘The selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945)’. Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to substitute the D2020 of Klose with D98-25BS because Sigma1 teaches that D98-25BS is a suitable replacement for the discontinued D2020.
Claim 20: Klose in view of Lokesh, Rijnaarts, and Nelson teaches that the proton conducting ionomer in the continuous nonporous hydrogen recombination catalyst coating layer comprises a perfluorosulfonic acid (PFSA) polymer (Nafion, see e.g. Klose - page F1272, col 1, paragraph starting with “In order”). However, Klose does not explicitly disclose using a form of Nafion claimed in claim 7. Klose teaches using D2020 see e.g. Klose - page F1272, col 1, paragraph starting with “In order”). The product page for D2020 says it has been discontinued and recommends using D98-25BS (see e.g. Sigma1). D98-25BS comprises a perfluorosulfonic acid (PFSA) polymer selected from copolymer of tetrafluoroethylene and perfluoro-3-oxa-4-pentene-sulfonic acid (see e.g. Sigma2). MPEP § 2144.07 states ‘The selection of a known material based on its suitability for its intended use supported a prima facie obviousness determination in Sinclair & Carroll Co. v. Interchemical Corp., 325 U.S. 327, 65 USPQ 297 (1945)’. Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to substitute the D2020 of Klose with D98-25BS because Sigma1 teaches that D98-25BS is a suitable replacement for the discontinued D2020.
Claim(s) 8, 9, and 16 is/are rejected under 35 U.S.C. 103 as being unpatentable over Klose in view of Lokesh, Rijnaarts, and Nelson as applied to claims 1, 10, and 14 above, and in further view of Bruix et al (“A New Type of Strong Metal–Support Interaction and the Production of H2 through the Transformation of Water on Pt/CeO2(111) and Pt/CeOx/TiO2(110) Catalysts”, J. Am. Chem. Soc. 2012, 134, 21, 8968–8974).
Claim 8: Klose in view of Lokesh, Rijnaarts, and Nelson does not explicitly teach that the continuous nonporous hydrogen recombination catalyst coating layer further comprises a radical scavenger. Bruix teaches a catalyst for the electrolysis of water, making it analogous art (see MPEP § 2141.01(a) I). Bruix teaches that adding CeO2 to a platinum catalyst (see e.g. abstract) “significantly enhance the ability of the admetal to adsorb water and dissociate the O−H bonds in the molecule” (see e.g. page 8973, col 2, paragraph starting with “The results”). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to modify the membrane of Klose to include the CeO2 additive taught in Bruix to enhance the ability of the metal to adsorb water and dissociate the O−H bonds in the molecule.
Claim 9: Klose in view of Lokesh, Rijnaarts, Nelson, and Bruix teaches that the additive comprises CeO2 (see e.g. Bruix – abstract).
Claim 16: Klose in view of Lokesh, Rijnaarts, and Nelson does not explicitly teach that the continuous nonporous hydrogen recombination catalyst coating layer further comprises a radical scavenger. Bruix teaches a catalyst for the electrolysis of water, making it analogous art (see MPEP § 2141.01(a) I). Bruix teaches that adding CeO2 to a platinum catalyst (see e.g. abstract) “significantly enhance the ability of the admetal to adsorb water and dissociate the O−H bonds in the molecule” (see e.g. page 8973, col 2, paragraph starting with “The results”). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the instant invention to modify the method of Klose to include the CeO2 additive taught in Bruix to enhance the ability of the metal to adsorb water and dissociate the O−H bonds in the molecule.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALEXANDER W KEELING whose telephone number is (571)272-9961. The examiner can normally be reached 7:30 AM - 4:00 PM. Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice. If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Luan Van can be reached at 571-272-8521. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/ALEXANDER W KEELING/Primary Examiner, Art Unit 1795
