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 § 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 1-4, 7-9, 11-12, 14 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Wu et al. (US 2021/0115577 A1).
Regarding claim 1, Wu et al. teaches a method for electrochemically reducing carbon dioxide, by exposing a gas comprising CO2 to a tandem electrode (corresponding to providing a vapor flow of CO2 to the tandem electrocatalyst) (paragraph [0006]). A voltage is applied to the tandem electrode (paragraph [0006]). The electrode is a tandem gas diffusion electrode (paragraph [0035]). The catalyst converts to C1 or C2+ products which include CH4, C2H4, C3H7OH, C2H5OH, CH3COO- and HCOO- (corresponding to direct conversion to carbon based molecule) (paragraph [0035]).
Regarding claim 2, Wu et al. teaches the first distinct catalyst layer is Cu, Cu alloys, doped Cu, nitrogen doped carbon materials (paragraph [0005]). In one embodiment the second distinct catalyst layer is selected from the group consisting of Au, Ag, ZnO, Fe-N-C, Ni-N-C, Co-N-C, doped CNT (carbon nanotubes), doped graphene and other materials (paragraph [0005]). The catalyst converts to C1 or C2+ products which include CH4, C2H4, C3H7OH, C2H5OH, CH3COO- and HCOO- (corresponding to direct conversion to carbon based molecule) (paragraph [0035]).
Regarding claim 3, the electrode is synthesized from commercial Cu nanoparticles (paragraphs [0044], [0047]).
Regarding claim 4, Wu et al. teaches the first distinct catalyst layer is Cu, Cu alloys (corresponding to binary or ternary alloy), doped Cu, nitrogen doped carbon materials (paragraph [0005]). In one embodiment the second distinct catalyst layer is selected from the group consisting of Au, Ag, ZnO, Fe-N-C, Ni-N-C, Co-N-C, (corresponding to a) nitrogen doped carbon) doped CNT (carbon nanotubes), doped graphene and other materials (paragraph [0005]).
Regarding claim 7, the electrode is made from commercial Cu nanoparticles (paragraphs [0044], [0047]).
Regarding claim 8 and 9, Wu et al. teaches in one embodiment the second distinct catalyst layer is selected from the group consisting of Au, Ag, ZnO, Fe-N-C, Ni-N-C, Co-N-C, doped CNT (carbon nanotubes), doped graphene and other materials (paragraph [0005]).
Regarding claim 11, Wu et al. teaches nitrogen doped carbon, with the second group consisting of Fe-N-C, Ni-N-C, and Co-N-C (paragraph [0005]). In some embodiments the range of catalyst layer thickness is from about 10 nm to about 50 microns (paragraph [0041]). It is the position of the examiner 10 nm catalyst layer would meet the classification of other nanostructure as stated in the instant claims.
Regarding claim 12, Wu et al. teaches the catalyst converts to C1 or C2+ products which include CH4, C2H4, C3H7OH, C2H5OH, CH3COO- and HCOO- (corresponding to direct conversion to carbon based molecule) (paragraph [0035]).
Regarding claim 14, Wu et al. teaches a tandem gas diffusion electrode, with two distinct catalyst layers operated in a flow cell (corresponding to flow electrolyte electrolyzer) (paragraph [0033]-[0034]).
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.
Claims 5-6 are rejected under 35 U.S.C. 103 as being unpatentable over Wu et al. (US 2021/0115577 A1) as applied to claims 1-4, 7-9, 11-12, 14 above, and further in view of Watanabe, M et al. Design of Alloy Electrocatalysts for CO2 Reduction. J. Electrochem. Soc. 1991, 138, 3382-3389.
Regarding claims 5 and 6, Wu et al. teaches the copper layer is Cu, Cu alloys, doped Cu. The presence of an alloy suggests Cu with the addition of Zn, Sn, Al, Si, and Ni, but Wu et al. does not teach the exact formulation of the copper alloy.
However, Watanabe et al. teaches Cu alloys for the electrocatalytic reduction of CO2 (abstract). Watanabe teaches Cu-Sn and Cu-Pb produce HCOOH and CO with enhanced reaction rate at reversible potentials for formation, and other alloy catalysts such as Cu-Zn, Cu-Cd, and Cu-Ag which exhibit behaviors distinct from those of elemental metals (abstract).
Therefore, it would have been prima facie obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have combined the teachings of Wu et al. with Watanabe et al. and use the specific copper alloys, Cu-Ag, Cu-Zn, Cu-Sn as the copper alloy in the composition as taught by Wu et al.
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Wu et al. (US 2021/0115577 A1) as applied to claim 1-4, 7-9, 11-12, 14 above, and further in view of Chen (US 2013/0048506 A1).
Regarding claim 10, Wu et al. teaches nitrogen doped carbon, with the second group consisting of Fe-N-C, Ni-N-C, and Co-N-C (paragraph [0005]), but does not teach porphyrins or phthalocyanines with modified ligands.
However, Chen teaches a method for converting CO2 to methanol, methane, and other hydrocarbons in an electrocatalytic cell, that includes a substrate with a metal plated thereon, and applying electricity to the electrolytical cell to reduce the CO2 (paragraph [0028]). The metals can be selected from Pt, Au, Ag, Zn, Co, Pb, Ni, Pd, and Cu (paragraph [0028]). The electrolytic cell system can include a source of the metal porphyrin salt (paragraphs [0006], [0012], [0030]). Chen teaches the use of chlorophyllin as a porphyrin, and is characterized by anodic attraction, the reverse pulse plating of the electrode creates regions of chlorophyllin membranes covering dendritic structures, which creates additional diffusion limited growth of the dendrites on a smaller scale (paragraph [0034]). The anodic attraction of chlorophyllin resulted in further branching of the nucleating copper particles as shown in SEM imaging (paragraph [0058]). Cyclic voltammetry studies supported the idea the chlorophyllin increases the resistivity of the system by preventing the flow of ions (paragraph [0058]).
Therefore, it would have been prima facie obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have combined the teachings of Wu et al. with Chen and use the porphyrins taught by Chen with the tandem electrocatalyst as taught by Wu et al. for the purpose as taught by Chen in order to increase the resistivity of the system by preventing the flow of ions, and increase the branching of the nucleating copper particles.
Claim 13 is rejected under 35 U.S.C. 103 as being unpatentable over Wu et al. (US 2021/0115577 A1) as applied to claims 1-4, 7-9, 11-12, 14 above, and further in view of Dongjin Kim, Woong Choi, Hee Won Lee, Si Young Lee, Yongjun Choi, Dong Ki Lee, Woong Kim, Jonggeol Na, Ung Lee, Yun Jeong Hwang, Da Hye Won; Electrocatalytic Reduction of Low Concentrations of CO2 Gas in a Membrane Electrode Assembly Electrolyzer. ACS Energy Lett. 2021; 6 (10): 3488–3495.
Regarding claim 13, Wu et al. teaches a flow cell, but does not teach a membrane electrode assembly electrolyzer.
However, Kim et al. teaches CO2 reduction using membrane electrode assembly (MEA) electrolyzer using Ni-N/C catalysts (abstract). Kim teaches the suppression of the hydrogen evolution reaction (HER) is important to achieve high CO selectivity under low CO2 pressure (pg. 3491, col. 2). The HER activity can be controlled by extrinsic factors, such as the mass transport properties in the GDE (gas diffusion electrode) based cell (pg. 3491, col. 2). Kim et al. demonstrated this by observing the performance of Ag nanoparticles in comparison to Ni-N/C, by controlling the quantity of water and protons at the cathode by taking advantage of the features of the MEA, the proton source is supplied by water crossover through the polymer membrane from the aqueous anolyte to the cathode, and can be controlled by operating conditions, which is unlike the case for typical H-type and flow cells (pg. 3491, col. 2). The zero gap MEA and Ni-N/C was shown to be less sensitive to CO2 concentration (pg. 3492, col. 1).
Therefore, it would have been prima facie obvious to one having ordinary skill in the art before the effective filing date of the claimed invention to have combined the teachings of Wu et al. with Kim et al. and use the membrane electrode assembly electrolyzer with the Cu and Ni-N/C catalyst as taught by Wu et al. for the purpose as taught by Kim to create a more selective catalyst (CO2 reduction over HER) and to produce a system which is less sensitive to CO2 concentration.
Conclusion
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/H.E.K./ Examiner, Art Unit 1742 /CHRISTINA A JOHNSON/Supervisory Patent Examiner, Art Unit 1742
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