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 .
Continued Examination Under 37 CFR 1.114
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and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114.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 05/20/2026 has been entered.
Status of Rejections
The rejection(s) of claim(s) 2-4, 14-16, 26-27 and 33 is/are obviated by applicant’s cancellation.
All other previous rejections are withdrawn in view of applicant’s amendments.
New grounds of rejection are necessitated by applicant’s amendments.
Claims 1, 8-10, 12, 17-19, 21-25, 28-32 and 34-35 are pending and under consideration for this Office Action.
Claim Objections
Claims 31-32 are objected to because of the following informalities:
In claim 31, line 3, “poly(4-vinylpyridine) and has” should read “poly(4-vinylpyridine), has”.
In claim 32, line 3, “poly(4-vinylpyridine) and has” should read “poly(4-vinylpyridine), .
Appropriate correction is required.
Claim Rejections - 35 USC § 103
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
Claims 1, 8-10, 17 and 31 are rejected under 35 U.S.C. 103 as being unpatentable over Hinden et al. (U.S. Patent No. 4,454,169) in view of Tsou et al. (U.S. Patent No. 5,171,644).
Regarding claims 1, Hinden teaches an electrode comprising a catalyst (see e.g. Col. 1, lines 7-9, and Col. 3, lines 60-65) obtained by sintering a homogenous mixture comprising a cobalt derivative, a nitrogen-containing derivative and a carbon compound at 300°C to 400°C (see e.g. Claim 1, Col. 1, lines 59-62, Col. 2, lines 67-68, and Col. 3, lines 5-23, 35-36 and 44-46, heat treatment, i.e. sintering, at 300-400°C of catalyst precursors including metal catalyst such as Co, support particles such as graphite, and organic precursor polymer such as polyvinyl pyridine, the metal catalyst uniformly distributed within a matrix of the polymer and on the support particles, thereby forming a homogenous mixture).
Hinden does not explicitly teach the nitrogen-containing derivative being selected from the group consisting of poly(4-vinylpyridine) and poly(2,5-pyridine), but does teach it being a polyvinyl pyridine (see e.g. Col. 3, lines 35-36).
Tsou teaches a catalyst for use in electrochemical cells (see e.g. Abstract) formed by heating a mixture of a metal salt, a carbon support and a polymer such as poly(4-vinylpyridine) (see e.g. Col. 3, lines 39-46, and Col. 5, lines 54-63)
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the polyvinyl pyridine of Hinden to particularly be poly(4-vinylpyridine) as taught by Tsou as a suitable particular polyvinyl pyridine for use in a catalyst composition for an electrochemical cell. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results.
Hinden, as modified above, does not explicitly teach a content of the cobalt derived from the cobalt derivative in the homogeneous mixture being 0.5 mass% or more and 3.5 mass% or less, and a molar ratio of a nitrogen-containing aromatic ring of the nitrogen-containing derivative to the cobalt of the cobalt derivative (nitrogen-containing aromatic ring/cobalt) in the homogeneous mixture being 5 or more and 20 or less. Hinden does generally teach a content the metal element derived from the metal derivative in the homogeneous mixture being less than 10 mass% (see e.g. Hinden Col. 2, lines 34-38, small amount of platinum group metal incorporated with support preferably forming more than 90 wt%).
Tsou further teaches a molar ratio of one of the pyridine repeating units in the polyvinylpyridine to the metal salt is preferably 4 to 20 (see e.g. Tsou Col. 3, lines 31-34, atomic ratio of metal to pyridine unit preferably 0.05 to 0.25, equal to a pyridine to metal ratio of 4 to 20), overlapping the claimed range of the present invention, as well as a specific example of cobalt having a 0.6 mass% concentration in the mixture of cobalt, polypyridine and carbon (see e.g. Tsou Col. 5, lines 54-63, 25 mL of 10 mmol CoCl2, equal to 0.032g CoCl2, 25 mL of 0.8 g/100mL poly(4-vinylpyridine) which equals 0.2 g, and 2g of carbon).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the catalyst of modified Hinden to have a pyridine ring to metal element ratio of 4 to 20 and a cobalt content of 0.6 mass% in the catalyst mixture as taught by Tsou as a suitable cobalt metal content and preferable ratio for a catalyst comprising cobalt, a carbon support and a polypyridine for use in electrochemical cells. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results. MPEP § 2144.05 I states “In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists.”
The limitation of “the electrode [being] a cathode” is a statement of intended use. MPEP § 2114 states “"[A]pparatus claims cover what a device is, not what a device does."…A claim containing a "recitation with respect to the manner in which a claimed apparatus is intended to be employed does not differentiate the claimed apparatus from a prior art apparatus" if the prior art apparatus teaches all the structural limitations of the claim.”. Modified Hinden teaches all the structural limitations of the claimed electrode as stated above. Hinden further teaches the electrode generally being used for electrocatalytic processes (see e.g. Col. 1, lines 7-9, and Col. 3, lines 60-65). The electrode of modified Hinden would therefore be capable of use as a cathode.
Regarding claim 8, Hinden as modified by Tsou above does not teach the carbon compound being carbon black, instead only exemplifying it as graphite (see e.g. Hinden Col. 2, lines 67-68). Hinden does however teach the carbon compound being a support for the metal catalyst (see e.g. Hinden Col. 2, lines 30-34).
Tsou further teaches electrically conductive support materials for the electrode catalyst including graphite or carbon powders, i.e. carbon black (see e.g. Tsou Col. 2, lines 41-43, Col. 3, lines 8-11, and Col. 5, lines 63-64).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the carbon compound of modified Hinden to comprise carbon powders, i.e. carbon black, instead of graphite as taught by Tsou as an alternate suitable electrically conductive carbon support for electrode catalyst materials. MPEP § 2143(I)(B) states that “simple substitution of one known element for another to obtain predictable results” may be obvious. 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)”.
Regarding claim 9, the limitation of the catalyst being a catalyst “for carbon dioxide reduction” is a statement of intended use. MPEP § 2114 states “"[A]pparatus claims cover what a device is, not what a device does."…A claim containing a "recitation with respect to the manner in which a claimed apparatus is intended to be employed does not differentiate the claimed apparatus from a prior art apparatus" if the prior art apparatus teaches all the structural limitations of the claim.”. Modified Hinden teaches all the structural elements of the claimed catalyst as stated above, and further teaches the catalyst generally being used in an electrode for electrocatalytic processes (see e.g. Hinden Col. 3, lines 60-65). The catalyst of modified Hinden would therefore be capable of use for carbon dioxide reduction.
Regarding claim 10, Hinden teaches a method for producing an electrode comprising a catalyst (see e.g. Col. 1, lines 7-10, and Col. 3, lines 60-65), comprising sintering a homogeneous mixture comprising a cobalt derivative, a nitrogen-containing derivative and a carbon compound at 300°C to 400°C to obtain the catalyst (see e.g. Claim 1, Col. 1, lines 59-62, Col. 2, lines 67-68, and Col. 3, lines 5-23, 35-36 and 44-46, heat treatment, i.e. sintering, at 300-400°C of catalyst precursors including metal catalyst such as Co, support particles such as graphite, and organic precursor polymer such as polyvinyl pyridine, the metal catalyst uniformly distributed within a matrix of the polymer and on the support particles, thereby forming a homogenous mixture), and
attaching the catalyst to an electrode base material (see e.g. Col. 3, lines 60-65, catalyst particles fixed to electrode base).
Hinden does not explicitly teach the nitrogen-containing derivative being selected from the group consisting of poly(4-vinylpyridine) and poly(2,5-pyridine), but does teach it being a polyvinyl pyridine (see e.g. Col. 3, lines 35-36).
Tsou teaches a catalyst for use in electrochemical cells (see e.g. Abstract) formed by heating a mixture of a metal salt, a carbon support and a polymer such as poly(4-vinylpyridine) (see e.g. Col. 3, lines 39-46, and Col. 5, lines 54-63)
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the polyvinyl pyridine of Hinden to particularly be poly(4-vinylpyridine) as taught by Tsou as a suitable particular polyvinyl pyridine for use in a catalyst composition for an electrochemical cell. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results.
Hinden, as modified above, does not explicitly teach a content of the cobalt derived from the cobalt derivative in the homogeneous mixture being 0.5 mass% or more and 3.5 mass% or less, and a molar ratio of a nitrogen-containing aromatic ring of the nitrogen-containing derivative to the cobalt of the cobalt derivative (nitrogen-containing aromatic ring/cobalt) in the homogeneous mixture being 5 or more and 20 or less. Hinden does generally teach a content the metal element derived from the metal derivative in the homogeneous mixture being less than 10 mass% (see e.g. Hinden Col. 2, lines 34-38, small amount of platinum group metal incorporated with support preferably forming more than 90 wt%).
Tsou further teaches a molar ratio of one of the pyridine repeating units in the polyvinylpyridine to the metal salt is preferably 4 to 20 (see e.g. Tsou Col. 3, lines 31-34, atomic ratio of metal to pyridine unit preferably 0.05 to 0.25, equal to a pyridine to metal ratio of 4 to 20), overlapping the claimed range of the present invention, as well as a specific example of cobalt having a 0.6 mass% concentration in the mixture of cobalt, polypyridine and carbon (see e.g. Tsou Col. 5, lines 54-63, 25 mL of 10 mmol CoCl2, equal to 0.032g CoCl2, 25 mL of 0.8 g/100mL poly(4-vinylpyridine) which equals 0.2 g, and 2g of carbon).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the catalyst of modified Hinden to have a pyridine ring to metal element ratio of 4 to 20 and a cobalt content of 0.6 mass% in the catalyst mixture as taught by Tsou as a suitable cobalt metal content and preferable ratio for a catalyst comprising cobalt, a carbon support and a polypyridine for use in electrochemical cells. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results. MPEP § 2144.05 I states “In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists.”
The limitation of “the electrode [being] a cathode” is a statement of intended use. MPEP § 2114 states “"[A]pparatus claims cover what a device is, not what a device does."…A claim containing a "recitation with respect to the manner in which a claimed apparatus is intended to be employed does not differentiate the claimed apparatus from a prior art apparatus" if the prior art apparatus teaches all the structural limitations of the claim.”. Modified Hinden teaches all the structural limitations of the claimed electrode as stated above. Hinden further teaches the electrode generally being used for electrocatalytic processes (see e.g. Col. 1, lines 7-9, and Col. 3, lines 60-65). The electrode of modified Hinden would therefore be capable of use as a cathode.
Regarding claim 17, modified Hinden teaches an electrode base material attached to the catalyst (see e.g. Hinden Col. 3, lines 60-65, catalyst particles fixed to electrode base).
Regarding claim 31, Hinden as modified by Tsou teaches the nitrogen containing derivative being the pyridine derivative being poly(4-vinylpyridine), having a plurality of pyridine rings and having a weight-average molecular weight of 49,000 (see e.g. Hinden Col. 3, lines 35-36, polyvinyl pyridine polymer which comprises a plurality of pyridine units; see e.g. Tsou Col. 5, lines 57-59, poly(4-vinylpyridine) with molecular weight of 4.9x105), which is very close to, within 2% of, the claimed weight-average molecular weight range.
MPEP § 2144.05 I states “a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. ”.
Claims 18-19 and 21-24 are rejected under 35 U.S.C. 103 as being unpatentable over Hinden in view of Tsou, as applied to claim 17 above, and further in view of Ma et al. (U.S. 2020/0220185).
Regarding claim 18, modified Hinden teaches the electrode comprising the catalyst according to claim 17 as a first electrode (see e.g. Hinden Col. 3, lines 60-65, catalyst particles fixed to electrode base to function as electrocatalyst). Modified Hinden does not teach a laminated assembly comprising the first electrode, an ion exchange membrane and a second electrode in this order, but does teach the first electrode being used in electrocatalytic processes (see e.g. Hinden Col. 3, lines 60-65).
Ma teaches a carbon dioxide reduction apparatus (see e.g. Abstract) comprising a sandwiched, i.e. laminated, membrane electrode assembly having a cathode layer with a reduction catalyst, an anode layer with an oxidation catalyst for oxygen evolution, and a polymer electrolyte membrane therebetween, this assembly enabling ionic communication between the anode layer and cathode layer while preventing electronic communication, which would produce a short circuit (see e.g. Paragraphs 0112 and 0239, and Paragraph 0106, lines 7-9).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the first electrode of modified Hinden to be provided in a laminated assembly with a second electrode on the other side of a polymer electrolyte membrane as taught by Ma as a suitable apparatus for an electrocatalytic process that enables ionic communication between the two electrodes while preventing electronic communication, which would produce a short circuit. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results.
Regarding claim 19, Hinden as modified by Ma teaches the first electrode further comprising a catalyst additive (see e.g. Hinden Col. 3, lines 63-65, catalyst with binder for fixing to electrode base);
the ion exchange membrane being a cation exchange membrane, or the ion exchange membrane being an anion exchange membrane (see e.g. Ma Paragraph 0112, line 13, and Paragraph 0115, lines 1-4, PEM including ion-conducting polymer such as anion-conductor or cation-conductor).
Hinden as modified by Ma above does not explicitly teach the catalyst additive being a cation conducting compound when the membrane is a cation exchange membrane or an anion conducting compound when the membrane is an anion exchange membrane. Hinden does however teach it being an organic or inorganic binder (see e.g. Hinden Col. 3, lines 63-65).
Ma further teaches that an anode layer may include an oxidation catalyst and an ion-conducting polymer such as a cation-conductor or anion-conductor (see e.g. Ma Paragraph 0112, lines 10-11, and Paragraph 0115, lines 1-4), with examples of the ion-conducting polymer being a cation-conductor when the membrane is a cation exchange membrane (see e.g. Ma Paragraph 0132, lines 4-9) and being an anion-conductor when the membrane is an anion exchange membrane (see e.g. Ma Paragraph 0142)
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the laminate assembly of modified Hinden to comprise a cation conductor as the catalyst additive when the membrane is a cation exchange membrane or an anion conductor as the catalyst additive when the membrane is an anion exchange membrane as taught by Ma as a suitable organic polymer/binder material for the anode layer, i.e. first electrode, of the laminate assembly. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results.
Regarding claim 21, Hinden as modified by Ma teaches the second electrode comprising a second catalyst and a catalyst additive (see e.g. Ma Paragraph 0112, lines 7-8, cathode layer including reduction catalyst and ion-conducting polymer), and
the ion exchange membrane being an anion exchange membrane and the catalyst additive in the second electrode being an anion conducting compound (see e.g. Ma Paragraph 0142).
Regarding claim 22, Hinden as modified by Ma teaches the ion exchange membrane being a cation exchange membrane (see e.g. Ma Paragraph 0132, lines 6-9, membrane layer including cation-conducting polymer), and
the catalyst additive being a compound having a sulfonyl group (see e.g. Ma Paragraph 0132, lines 4-6, and Table on Pg. 13, Class C, anode layer including cation conducting polymer such as perfluorosulfonic acid polytetrafluoroethylene co-polymer, sulfonated poly(ether ether ketone), and poly(styrene sulfonic acid- co-maleic acid)).
Regarding claim 23, Hinden as modified by Ma teaches the ion exchange membrane being an anion exchange membrane (see e.g. Ma Paragraph 0142, lines 1-2, anion-exchange polymer electrolyte membrane), and
the catalyst additive having at least one functional group selected from the group consisting of an amino group and an ammonium group (see e.g. Ma Paragraph 0142, lines 3-5, and Table on Pg. 13, Class A, anode electrocatalyst layer with anion-exchange polymer electrolyte such as aminated tetramethyl polyphenylene and poly(ethylene-co-tetrafluoroethylene)-based quaternary ammonium polymer).
Regarding claim 24, Hinden as modified by Ma teaches a catalyst composition comprising the catalyst and the catalyst additive is held by the electrode base material in the first electrode (see e.g. Hinden Col. 3, lines 63-65, catalyst with binder for fixing to electrode base; see e.g. Ma Paragraph 0112, lines 10-11, anode layer including oxidation catalyst and ion-conducting polymer), and
a content of the catalyst additive in the catalyst composition being between 5 and 20 mass% or approximately 50 wt% (see e.g. Ma Paragraph 0216, lines 7-10).
Claims 12, 29-30 and 32 are rejected under 35 U.S.C. 103 as being unpatentable over Ma in view of Kaczur et al. (U.S. 2017/0037522), and further in view of Hinden and Tsou.
Regarding claim 12, Ma teaches a carbon dioxide reduction apparatus (see e.g. Paragraph 0018, lines 1-3, and Paragraph 0299, lines 6-9, COx, e.g. CO2, reduction reactor including MEAs) comprising an electrode comprising a catalyst (see e.g. Paragraph 0018, lines 4-5, cathode including COx reduction catalyst), the catalyst comprising cobalt (see e.g. Paragraph 0160, lines 1-3) and a carbon-support part (see e.g. Paragraph 0162, lines 1-2),
wherein the cobalt is supported on the carbon support part (see e.g. Paragraph 0159, lines 2-4, support particles providing support for catalyst particles), and
wherein the cobalt is formed in a particulate cobalt, and the particulate cobalt has an average particle size of 0.2 nm to 10 nm (see e.g. Paragraph 0161, lines 1-3), and
wherein the electrode is a cathode (see e.g. Paragraph 0018, line 4).
Ma does not explicitly teach the cobalt being in the form of cobalt oxide, but does generally teach that any suitable reduction catalyst materials can be used (see e.g. Paragraph 0160, lines 1-6).
Kaczur teaches an electrochemical device for converting carbon dioxide (see e.g. Abstract) comprising a cathode electrocatalyst including transition metals, their oxides and combinations thereof deposited on a conductive carrier such as carbon (see e.g. Paragraph 0236, lines 1-8).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the catalyst of Ma to alternately or additionally comprise the oxide of the cobalt transition metal as taught by Kaczur as a suitable cathode, i.e. reduction, catalyst for electrochemical conversion of carbon dioxide. 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)”.
Modified Ma does not teach the catalyst including a nitrogen-containing part, wherein the nitrogen containing part is in a homogenous mixture with the cobalt oxide and also supported on the carbon-support part, the nitrogen containing part is derived from at least one nitrogen-containing derivative, wherein the catalyst is obtained by heat-treating a homogeneous mixture of comprising a cobalt salt, the at least one nitrogen containing derivative, and a carbon compound at 300°C or more and 450°C or less.
Hinden teaches a catalyst for electrocatalytic processes (see e.g. Col. 3, lines 60-65) comprising a metal catalyst such as a cobalt or nickel uniformly distributed within a matrix of a polymer such as nitrogen-containing polyvinyl pyridine and on support particles such as graphite, thereby forming a homogenous mixture (see e.g. Claim 1, Col. 1, lines 59-62, Col. 2, lines 67-68, and Col. 3, lines 5-23 and 35-36), this catalyst structure providing a large catalytically active surface area (see e.g. Col. 1, lines 59-62), wherein the catalyst is obtained by heat treatment, i.e. sintering, at 300-400°C of catalyst precursors, i.e. derivatives, including the metal catalyst, support particles and precursor polymer in the homogenous mixture (see e.g. Claim 1, Col. 1, lines 59-62, Col. 2, lines 67-68, and Col. 3, lines 5-23, 35-36 and 44-46).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the catalyst of modified Ma to comprise the metal part, carbon compound and a nitrogen-containing polyvinyl pyridine obtained by sintering a homogeneous mixture of precursors thereof at 300-400°C as taught by Hinden to enable formation of a catalyst with a large catalytically active surface area.
Ma, as modified by Hinden above, does not explicitly teach the nitrogen-containing derivative being selected from the group consisting of poly(4-vinylpyridine) and poly(2,5-pyridine), but Hinden does teach it being a polyvinyl pyridine (see e.g. Hinden Col. 3, lines 35-36).
Tsou teaches a catalyst for use in electrochemical cells (see e.g. Abstract) formed by heating a mixture of a metal salt, a carbon support and a polymer such as poly(4-vinylpyridine) (see e.g. Col. 3, lines 39-46, and Col. 5, lines 54-63)
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the polyvinyl pyridine of modified Ma to particularly be poly(4-vinylpyridine) as taught by Tsou as a suitable particular polyvinyl pyridine for use in a catalyst composition for an electrochemical cell. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results.
Ma, as modified above, does not explicitly teach a content of the cobalt derived from the cobalt derivative in the homogeneous mixture being 0.5 mass% or more and 3.5 mass% or less, and a molar ratio of a nitrogen-containing aromatic ring of the nitrogen-containing derivative to the cobalt of the cobalt derivative (nitrogen-containing aromatic ring/cobalt) in the homogeneous mixture being 5 or more and 20 or less. Hinden does generally teach a content the metal element derived from the metal derivative in the homogeneous mixture being less than 10 mass% (see e.g. Hinden Col. 2, lines 34-38, small amount of platinum group metal incorporated with support preferably forming more than 90 wt%).
Tsou further teaches a molar ratio of one of the pyridine repeating units in the polyvinylpyridine to the metal salt is preferably 4 to 20 (see e.g. Tsou Col. 3, lines 31-34, atomic ratio of metal to pyridine unit preferably 0.05 to 0.25, equal to a pyridine to metal ratio of 4 to 20), overlapping the claimed range of the present invention, as well as a specific example of cobalt having a 0.6 mass% concentration in the mixture of cobalt, polypyridine and carbon (see e.g. Tsou Col. 5, lines 54-63, 25 mL of 10 mmol CoCl2, equal to 0.032g CoCl2, 25 mL of 0.8 g/100mL poly(4-vinylpyridine) which equals 0.2 g, and 2g of carbon).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the catalyst of modified Ma to have a pyridine ring to metal element ratio of 4 to 20 and a cobalt content of 0.6 mass% in the catalyst mixture as taught by Tsou as a suitable cobalt metal content and preferable ratio for a catalyst comprising cobalt, a carbon support and a polypyridine for use in electrochemical cells. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results. MPEP § 2144.05 I states “In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists.”
Regarding claim 29, modified Ma teaches an anode (see e.g. Ma Paragraph 0018, line 6) and a power source connected to the anode and the cathode, wherein a voltage is applied between the anode and the cathode (see e.g. Ma Fig. 1D, power source and controller 133 applied voltage to the electrodes, i.e. anode and cathode, of the reactor Paragraph 0018, lines 8-10, and Paragraph 0091), and an introduction port that introduces carbon dioxide into the apparatus so as to reduce the carbon dioxide by the catalyst on the first electrode (see e.g. Ma Paragraph 0006, lines 3-6, Paragraph 0096, lines 5-6, and Paragraph 0299, lines 6-9, cathode inlet to which COx, e.g. CO2, gas reactant is delivered to be reduced at the cathode).
Regarding claim 30, modified Ma teaches a method of reducing carbon dioxide (see e.g. Ma Paragraph 0006, lines 1-3, and Paragraph 0299, lines 6-9, method of operating MEA for COx, e.g. CO2, reduction), comprising reducing carbon dioxide by the catalyst in the carbon dioxide reduction apparatus of according to claim 12 (see e.g. Paragraph 0006, lines 3-6, and Paragraph 0158, COx, e.g. CO2, gas reduced at cathode comprising reduction catalysts).
Regarding claim 32, Ma as modified by Hinden and Tsou teaches the nitrogen containing derivative being the pyridine derivative being poly(4-vinylpyridine), having a plurality of pyridine rings and having a weight-average molecular weight of 49,000 (see e.g. Hinden Col. 3, lines 35-36, polyvinyl pyridine polymer which comprises a plurality of pyridine units; see e.g. Tsou Col. 5, lines 57-59, poly(4-vinylpyridine) with molecular weight of 4.9x105), which is very close to, within 2% of, the claimed weight-average molecular weight range.
MPEP § 2144.05 I states “a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close. ”.
Claim 28 is rejected under 35 U.S.C. 103 as being unpatentable over Ma, Kaczur, Hinden and Tsou, as applied to claim 12 above, and further in view of Chou et al. (U.S. 2018/0214945).
Regarding claim 28, Modified Ma teaches all the elements of the apparatus of claim 12 as stated above. Ma as modified by Kaczur further teaches the apparatus comprising a cobalt metal in the catalyst (see e.g. Ma Paragraph 0160, lines 1-3, Co as catalyst particle; see e.g. Kaczur Paragraph 0236, lines 6-8, electrocatalyst comprising combination of metals and oxides). Modified Ma does not teach the catalyst having a core-shell structure in which the cobalt metal serves as a core and the cobalt oxide is disposed around the core and covers the cobalt metal.
Chou teaches core@shell nanoparticles for use as electrocatalysts in electrochemical cells such as those for converting carbon dioxide (see e.g. Abstract), wherein the nanoparticles may comprise a catalytic core component including a metal such as cobalt in a solid core with an oxide of the metal coating the solid core (see e.g. Paragraphs 0039-0041 and 0100), the formation of the metal oxide layer on the outer surface of the metal core improving selectivity and catalytic activity of the core-shell catalyst in an electrochemical cell for conversion of carbon dioxide to an organic feedstock (see e.g. Paragraph 0101).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the catalyst of modified Ma to comprise a core-shell structure with the cobalt metal as a core covered by a layer of the cobalt oxide as taught by Chou to improve selectivity and activity of the catalyst in electrochemical conversion of carbon dioxide.
Claims 25 and 34-35 are rejected under 35 U.S.C. 103 as being unpatentable over Ma in view of Hinden, and further in view of Tsou.
Regarding claim 25, Ma teaches a carbon dioxide reduction apparatus (see e.g. Paragraph 0018, lines 1-3, and Paragraph 0299, lines 6-9, COx, e.g. CO2, reduction reactor including MEA) comprising an electrode comprising a catalyst (see e.g. Paragraph 0018, lines 4-5, cathode including COx reduction catalyst), wherein the catalyst comprises a cobalt part (see e.g. Paragraph 0160, lines 1-3) and a carbon compound (see e.g. Paragraph 0162, lines 1-2), and
wherein the electrode is a cathode (see e.g. Paragraph 0018, line 4).
Ma does not teach the catalyst being obtained by sintering a homogenous mixture comprising a cobalt derivative which forms the cobalt part, at least one nitrogen-containing derivative and the carbon compound at 300°C or more and 450°C or less.
Hinden teaches a catalyst for electrocatalytic processes (see e.g. Col. 3, lines 60-65) comprising a metal catalyst such as a cobalt or nickel uniformly distributed within a matrix of a polymer such as nitrogen-containing polyvinyl pyridine and on support particles such as graphite, thereby forming a homogenous mixture (see e.g. Claim 1, Col. 1, lines 59-62, Col. 2, lines 67-68, and Col. 3, lines 5-23 and 35-36), this catalyst structure providing a large catalytically active surface area (see e.g. Col. 1, lines 59-62), wherein the catalyst is obtained by heat treatment, i.e. sintering, at 300-400°C of catalyst precursors, i.e. derivatives, including the metal catalyst, support particles and precursor polymer in the homogenous mixture (see e.g. Claim 1, Col. 1, lines 59-62, Col. 2, lines 67-68, and Col. 3, lines 5-23, 35-36 and 44-46).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the catalyst of modified Ma to comprise the metal part, carbon compound and a nitrogen-containing polyvinyl pyridine obtained by sintering a homogeneous mixture of precursors thereof at 300-400°C as taught by Hinden to enable formation of a catalyst with a large catalytically active surface area.
Ma, as modified by Hinden above, does not explicitly teach the nitrogen-containing derivative being selected from the group consisting of poly(4-vinylpyridine) and poly(2,5-pyridine), but Hinden does teach it being a polyvinyl pyridine (see e.g. Hinden Col. 3, lines 35-36).
Tsou teaches a catalyst for use in electrochemical cells (see e.g. Abstract) formed by heating a mixture of a metal salt, a carbon support and a polymer such as poly(4-vinylpyridine) (see e.g. Col. 3, lines 39-46, and Col. 5, lines 54-63)
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the polyvinyl pyridine of modified Ma to particularly be poly(4-vinylpyridine) as taught by Tsou as a suitable particular polyvinyl pyridine for use in a catalyst composition for an electrochemical cell. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results.
Ma, as modified above, does not explicitly teach a content of the cobalt derived from the cobalt derivative in the homogeneous mixture being 0.5 mass% or more and 3.5 mass% or less, and a molar ratio of a nitrogen-containing aromatic ring of the nitrogen-containing derivative to the cobalt of the cobalt derivative (nitrogen-containing aromatic ring/cobalt) in the homogeneous mixture being 5 or more and 20 or less. Hinden does generally teach a content the metal element derived from the metal derivative in the homogeneous mixture being less than 10 mass% (see e.g. Hinden Col. 2, lines 34-38, small amount of platinum group metal incorporated with support preferably forming more than 90 wt%).
Tsou further teaches a molar ratio of one of the pyridine repeating units in the polyvinylpyridine to the metal salt is preferably 4 to 20 (see e.g. Tsou Col. 3, lines 31-34, atomic ratio of metal to pyridine unit preferably 0.05 to 0.25, equal to a pyridine to metal ratio of 4 to 20), overlapping the claimed range of the present invention, as well as a specific example of cobalt having a 0.6 mass% concentration in the mixture of cobalt, polypyridine and carbon (see e.g. Tsou Col. 5, lines 54-63, 25 mL of 10 mmol CoCl2, equal to 0.032g CoCl2, 25 mL of 0.8 g/100mL poly(4-vinylpyridine) which equals 0.2 g, and 2g of carbon).
It would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to have modified the catalyst of modified Ma to have a pyridine ring to metal element ratio of 4 to 20 and a cobalt content of 0.6 mass% in the catalyst mixture as taught by Tsou as a suitable cobalt metal content and preferable ratio for a catalyst comprising cobalt, a carbon support and a polypyridine for use in electrochemical cells. MPEP § 2143(I)(A) states that “combining prior art elements according to known methods to yield predictable results” may be obvious. The claimed elements were known in the prior art and one skilled in the art could have combined the elements as claimed by known methods with no change in their respective functions, and the combination would yield nothing more than predictable results. MPEP § 2144.05 I states “In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists.”
Regarding claim 34, modified Ma teaches the carbon dioxide reduction apparatus further comprising an anode (see e.g. Ma Paragraph 0018, line 6) and a power source connected to the anode and the cathode, wherein a voltage is applied between the anode and the cathode (see e.g. Ma Fig. 1D, power source and controller 133 applied voltage to the electrodes, i.e. anode and cathode, of the reactor Paragraph 0018, lines 8-10, and Paragraph 0091), and
an introduction port that introduces carbon dioxide into the apparatus so as to reduce the carbon dioxide by the catalyst on the cathode (see e.g. Ma Paragraph 0006, lines 3-6, Paragraph 0096, lines 5-6, and Paragraph 0299, lines 6-9, cathode inlet to which COx, e.g. CO2, gas reactant is delivered to be reduced at the cathode).
Regarding claim 35, modified Ma teaches the carbon compound being carbon black (see e.g. Ma Paragraphs 0204 and 0207-210).
Response to Arguments
Applicant’s arguments, see pages 11-14, filed 05/20/2026, with respect to the rejection(s) of claim(s) 1 and 10 under 35 USC 103 over Hinden in view of Hatton, particularly regarding the specific nitrogen-containing derivative and the unexpected results of the narrower cobalt mass% range, have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Hinden and Tsou.
Applicant’s arguments, see pages 11-14, filed 05/20/2026, with respect to the rejection(s) of claim(s) 12 under 35 USC 103 over Ma, Kaczur, Hinden and Hatton, particularly regarding the specific nitrogen-containing derivative and the unexpected results of the narrower cobalt mass% range, have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Ma, Kaczur, Hinden and Tsou.
Applicant’s arguments, see pages 11-14, filed 05/20/2026, with respect to the rejection(s) of claim(s) 25 under 35 USC 103 over Ma, Hinden and Hatton, particularly regarding the specific nitrogen-containing derivative and the unexpected results of the narrower cobalt mass% range, have been fully considered and are persuasive. Therefore, the rejection has been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of Ma, Hinden and Tsou.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant's disclosure.
Schiavon et al. (“Easy preparation of electrodes modified by conjugated polypyridine films displaying coordinative properties and their effectiveness as mediators of electrocatalytic processes”, J. Electroanal. Chem., 1988) discloses an electrode coated by poly-2,5-pyridine to mediate electrocatalytic processes.
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/MOFOLUWASO S JEBUTU/Examiner, Art Unit 1795
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