DETAILED ACTION
Notice of Pre-AIA or AIA Status
1. The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 102
2. 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.
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
3. Claims 1, 3, 7, 8, 9, and 10 are rejected under 35 U.S.C. 102(a)(1) as being anticipated by Zhang et al.
Zhang et al. (“Fabrication of Novel Ternary Three-Dimensional RuO2/Graphitic-C3N4@reduced Graphene Oxide Aerogel Composites for Supercapacitors,” ACS Sustainable Chem. Eng. 2017, 5(6), 4982-4991 and supporting information) is directed toward a 3D ternary composite (pg. 4982: title and abstract).
Regarding Claim 1, Zhang et al. discloses a device (an asymmetric supercapacitor device on pg. 4983 in section 2.5 Electrochemical Measurements) comprising: an electrode (Ni-foam coated with active material, carbon black, and Nafion polymer on pg. 4983 in section 2.5 Electrochemical Measurements). The active material of Zhang et al. is abbreviated RCGA and is short for 3D RuO2/g-C3N4@reduced graphene oxide (rGO) aerogel composite (pg. 4982: abstract). The electrode of Zhang et al. further discloses the active material of the electrode is prepared (pg. 2.3 Synthesis of RCGA, RGA and GA) using ruthenium oxide (analogous to the ruthenium ions of Claim 1), protonated g-C3N4 and graphene oxide (“GO”). The mixture is then heated in a sealed vessel and at 150 °C (analogous to refluxing of Claim 1). Zhang et al. further discloses that GO is completely reduced to rGO as per XRD analysis (pg. 4986) during the refluxing step.
Regarding Claim 3, Zhang et al. discloses the device of Claim 1, wherein the g-C3N4-rGO nanosheet is formed by: incorporating graphene oxide (GO) in a solution; reducing the graphene oxide (rGO) by refluxing the carbon nitride in the solution as supported by section 2.3 Synthesis of RCGA, RGA, and GA on pg. 4983.
Regarding Claim 7, Zhang et al. discloses the device of Claim 1, wherein XPS measurements are performed on the C3N4-rGO nanosheet as evidenced by Figure 4a (pg. 4986).
Regarding Claim 8, Zhang et al. discloses the device of Claim 1, wherein TEM is performed on the C3N4-rGO nanosheet as evidenced by Figure S2 on pg. 3 of the supporting information.
Regarding Claim 9, Zhang et al. discloses the device of Claim 3, wherein the solution is an aqueous solution as supported by section 2.3 Synthesis of RCGA, RGA, and GA on pg. 4983.
Regarding Claim 10, Zhang et al. discloses the device of Claim 9, wherein the aqueous solution is water as supported by section 2.3 Synthesis of RCGA, RGA, and GA on pg. 4983.
Claim Rejections - 35 USC § 103
4. The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
5. Claim 2 is rejected under 35 U.S.C. 103 as being unpatentable over Zhang et al. as applied to Claim 1 above, and further in view of Rovetta et al.
Zhang et al. (“Fabrication of Novel Ternary Three-Dimensional RuO2/Graphitic-C3N4@reduced Graphene Oxide Aerogel Composites for Supercapacitors,” ACS Sustainable Chem. Eng. 2017, 5(6), 4982-4991 and SI) is directed toward a 3D ternary composite (pg. 4982: title and abstract). Rovetta et al. (“Cobalt hydroxide nanoflakes and their application as supercapacitors and oxygen evolution catalysts,” Nanotech. 2017, 28, article 375401, pg. 1-12) is directed toward Co-based supercapacitors (pg. 1: title and abstract).
Regarding Claim 2, Zhang et al. discloses the device of Claim 1, wherein the electrode is a nickel-based electrode, not a glassy carbon electrode as required by Claim 2. Rovetta et al. is directed toward metal hydroxide nanoflakes in supercapacitors (pg. 1: title and abstract). Rovetta further discloses that active material was deposited onto either nickel foam or glassy carbon (pg. 2: introduction and pg. 4: 3.1 physical characterization). Rovetta et al. teaches that comparing the stabilities of the uncoated electrodes in alkaline media reveals that glassy carbon has no inherent electrical activity whereas Ni foam undergoes Ni(II)/Ni(III) redox shuffling (pg. 5). The low inherent redox activity of GC would make it a preferred substrate for general use. It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to substitute the GC electrode of Rovetta for the nickel support of Zhang et al. to form a more electrode support for use in supercapacitor applications.
6. Claim 6 is rejected under 35 U.S.C. 103 as being unpatentable over Zhang et al. as applied to Claim 1 above, and further in view of Aleksandrzak et al.
Zhang et al. (“Fabrication of Novel Ternary Three-Dimensional RuO2/Graphitic-C3N4@reduced Graphene Oxide Aerogel Composites for Supercapacitors,” ACS Sustainable Chem. Eng. 2017, 5(6), 4982-4991 and supporting information) is directed toward a 3D ternary composite (pg. 4982: title and abstract). Aleksandrzak et al. (“Graphitic carbon nitride/graphene oxide/reduced graphene oxide nanocomposites for photoluminescence and photocatalysis,” Appl. Surf. Sci. 2017, 398, 56-62) is directed toward graphitic nanocomposites (pg. 89: title).
Regarding Claim 6, Zhang et al. discloses the device of Claim 1, wherein the formed C3N4-rGO nanosheet is confirmed by multiple analytical techniques, but does not explicitly use AFM. Aleksandrzak et al. discloses the use of multiple analytical techniques for characterizing graphitic nitride (g-C3N4) modified by rGO (see pg. 57: 2.1.4. for synthesis), such as AFM, TEM, XRD, FT-IR among others to characterize the graphitic nanomaterials (pg. 56: abstract). Aleksandrzak et al. specifically indicates that AFM is useful for determining the number of layers stacked to make the g-C3N4-rGO composite and also to characterize the topology the composite (pg. 57-58: 3. Results and Discussion) as rGO and the composite have different sizes lengths and flatness.
Since Zhang et al. and Aleksandrzak et al. are directed toward g-C3N4-rGO-based composites, applying all of the analytical methods would be obvious to one of ordinary skill in the art. Prior to the effective filing date of the claimed invention, the skilled artisan could reasonably be expected use AFM measurements as indicated by Aleksandrzak et al. on the Ru-modified g-C3N4-rGO composite of Zhang et al. with the reasonable expectation of being able to characterize said composite to confirm the formation of C3N4-rGO nanosheets.
7. Claims 1, 3, 11, 13, 17, 18, 19, and 20 are rejected under 35 U.S.C. 103 as being unpatentable over Zhang et al. in view of Lee et al.
Zhang et al. (“Fabrication of Novel Ternary Three-Dimensional RuO2/Graphitic-C3N4@reduced Graphene Oxide Aerogel Composites for Supercapacitors,” ACS Sustainable Chem. Eng. 2017, 5(6), 4982-4991 and SI) is directed toward a 3D ternary composite (pg. 4982: title and abstract). Lee et al. (“Hydrous RuO2 nanoparticles as highly active electrocatalysts for hydrogen evolution reaction,” Chem. Phys. Lett. 2017, 673, 89-92) is directed toward ruthenium oxide nanoparticles for HER (pg. 89: title and abstract).
Regarding Claim 1, Zhang et al. discloses an electrode (Ni-foam coated with active material, carbon black, and Nafion on pg. 4983 in section 2.5 Electrochemical Measurements). The active material of Zhang et al. is abbreviated RCGA and is short for 3D RuO2/g-C3N4@reduced graphene oxide (rGO) aerogel composite (pg. 4982: abstract). The electrode of Zhang et al. further discloses the active material of the electrode is prepared (pg. 2.3 Synthesis of RCGA, RGA and GA) using ruthenium oxide (analogous to the ruthenium ions of Claim 1), protonated g-C3N4 and GO. The mixture is then heated in a sealed vessel and at 150 °C (analogous to refluxing of Claim 1). Zhang et al. further discloses that GO is completely reduced to rGO as per XRD analysis (pg. 4986) during the reflux step. However, Zhang et al. does not disclose the use of RuO2 as a catalyst.
Lee et al. indicates that RuO2 is used as both an active material in supercapacitors and an active hydrogen evolution catalyst (pg. 89: introduction). Lee et al. further discloses an electrode composition comprising the RuO2 catalyst (made from RuCl3), Ketjen black, and PVDF (pg. 90: electrochemical measurements) deposited onto nickel foam. Lee et al. discloses the use of the RuO2 electrode in an electrochemical cell (i.e.: a device on pg. 90: 2.3. Electrochemical measurements). Since both Lee et al. and Zhang et al. have ruthenium-based catalysts that exhibit supercapacitor activity, they are in the same field of art.
It would be obvious to one of ordinary skill in the art that prior to the effective filing date of the claimed invention to use the RuO2/g-C3N4@reduced graphene oxide composite material of Zhang et al. as the active material in the electrode of Lee et al. with the reasonable expectation of forming a highly active HER catalyst since the composite of Zhang et al. will have enhanced electrical conductivity given the stacked parallel sheet structure (pg.4984: Scheme 1 of Zhang et al.).
Regarding Claim 3, Zhang et al. in view of Lee et al. disclose the device of Claim 1, wherein the g-C3N4-rGO nanosheet is formed by: incorporating graphene oxide (GO) in a solution; reducing the graphene oxide (rGO) by refluxing the carbon nitride in the solution as supported by section 2.3 Synthesis of RCGA, RGA, and GA on pg. 4983.
Regarding Claim 11, Zhang et al. discloses an electrode (Ni-foam coated with active material, carbon black, and Nafion on pg. 4983 in section 2.5 Electrochemical Measurements). The active material of Zhang et al. is abbreviated RCGA and is short for 3D RuO2/g-C3N4@reduced graphene oxide (rGO) aerogel composite (pg. 4982: abstract). The electrode of Zhang et al. further discloses the active material of the electrode is prepared (pg. 2.3 Synthesis of RCGA, RGA and GA) using ruthenium oxide (analogous to the ruthenium ions of Claim 11), protonated g-C3N4 and graphene oxide. The mixture is then heated in a sealed vessel and at 150 °C (analogous to refluxing of Claim 11). Zhang et al. further discloses that GO is completely reduced to rGO as per XRD analysis (pg. 4986). However, Zhang et al. does not disclose the use of RuO2 as a catalyst.
Lee et al. indicates that RuO2 is used as both an active material in supercapacitors and an active hydrogen catalyst (pg. 89: introduction). Lee et al. further discloses an electrode composition comprising the RuO2 catalyst (made from RuCl3), Ketjen black, and PVDF (pg. 90: electrochemical measurements) deposited onto nickel foam. Lee et al. discloses the use of the RuO2 electrode in an electrochemical cell (i.e.: a device on pg. 90: 2.3. Electrochemical measurements). Since both Lee et al. and Zhang et al. have ruthenium-based catalysts that exhibit supercapacitor activity, they are in the same field of art.
It would be obvious to one of ordinary skill in the art that prior to the effective filing date of the claimed invention to use the RuO2/g-C3N4@reduced graphene oxide composite material of Zhang et al. as the active material in the electrode of Lee et al. with the reasonable expectation of forming a highly active HER catalyst since the composite of Zhang et al. will have enhanced electrical conductivity given the stacked parallel sheet structure (pg.4984: Scheme 1 of Zhang et al.).
Regarding Claim 13, Zhang et al. in view of Lee et al. disclose the catalytic material of Claim 11, wherein the g-C3N4-rGO nanosheet is formed by: incorporating graphene oxide (GO) in a solution; reducing the graphene oxide (rGO) by refluxing the carbon nitride in the solution as supported by section 2.3 Synthesis of RCGA, RGA, and GA on pg. 4983.
Regarding Claim 17, Zhang et al. in view of Lee et al. the device of Claim 11, wherein XPS measurements are performed on the C3N4-rGO nanosheet as evidenced by Figure 4a (pg. 4986).
Regarding Claim 18, Zhang et al. in view of Lee et al. disclose the catalytic material of Claim 11, wherein TEM analysis is performed on the C3N4-rGO nanosheet as evidenced by Figure S2 on pg. 3 of the supporting information.
Regarding Claim 19, Zhang et al. in view of Lee et al. disclose the catalytic material of Claim 13, wherein the solution is an aqueous solution as supported by section 2.3 Synthesis of RCGA, RGA, and GA on pg. 4983.
Regarding Claim 20, Zhang et al. in view of Lee et al. disclose the catalytic material of Claim 19, wherein the aqueous solution is water as supported by section 2.3 Synthesis of RCGA, RGA, and GA on pg. 4983.
8. Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Zhang et al. in view of Lee et al. as applied to Claim 11 above, and further in view of Rovetta et al.
Zhang et al. (“Fabrication of Novel Ternary Three-Dimensional RuO2/Graphitic-C3N4@reduced Graphene Oxide Aerogel Composites for Supercapacitors,” ACS Sustainable Chem. Eng. 2017, 5(6), 4982-4991 and SI) is directed toward a 3D ternary composite (pg. 4982: title and abstract). Lee et al. (“Hydrous RuO2 nanoparticles as highly active electrocatalysts for hydrogen evolution reaction,” Chem. Phys. Lett. 2017, 673, 89-92) is directed toward ruthenium oxide nanoparticles for HER (pg. 89: title and abstract). Rovetta et al. (“Cobalt hydroxide nanoflakes and their application as supercapacitors and oxygen evolution catalysts,” Nanotech. 2017, 28, article 375401, pg. 1-12) is directed toward Co-based supercapacitors (pg. 1: title and abstract).
Regarding Claim 12, Zhang et al. in view of Lee et al. discloses the catalytic material of Claim 11, wherein the electrode is a nickel-based electrode, not a glassy carbon electrode as required by Claim 12. Rovetta et al. is directed toward metal hydroxide nanoflakes in supercapacitors (pg. 1: title and abstract). Rovetta further discloses that active material was deposited onto either nickel foam or glassy carbon (pg. 2: introduction and pg. 4: 3.1 physical characterization). Rovetta et al. teaches that comparing the stabilities of the uncoated electrodes in alkaline media reveals that glassy carbon has no inherent electrical activity whereas Ni foam undergoes Ni(II)/Ni(III) redox shuffling (pg. 5). The low inherent redox activity of GC would make it a preferred substrate for general use. It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to substitute the GC electrode of Rovetta for the nickel support of Zhang et al. in view of Lee et al. to form a more robust electrode.
9. Claim 16 is rejected under 35 U.S.C. 103 as being unpatentable over Zhang et al. in view of Lee et al. as applied to Claim 11 above, and further in view of Aleksandrzak et al.
Zhang et al. (“Fabrication of Novel Ternary Three-Dimensional RuO2/Graphitic-C3N4@reduced Graphene Oxide Aerogel Composites for Supercapacitors,” ACS Sustainable Chem. Eng. 2017, 5(6), 4982-4991 and supporting information) is directed toward a 3D ternary composite (pg. 4982: title and abstract). Lee et al. (“Hydrous RuO2 nanoparticles as highly active electrocatalysts for hydrogen evolution reaction,” Chem. Phys. Lett. 2017, 673, 89-92) is directed toward ruthenium oxide nanoparticles for HER (pg. 89: title and abstract). Aleksandrzak et al. (“Graphitic carbon nitride/graphene oxide/reduced graphene oxide nanocomposites for photoluminescence and photocatalysis,” Appl. Surf. Sci. 2017, 398, 56-62) is directed toward graphitic nanocomposites (pg. 89: title).
Regarding Claim 16, Zhang et al. in view of Lee et al. discloses the HER catalyst of Claim 11, wherein the formed C3N4-rGO nanosheet is confirmed by multiple analytical techniques, but does not explicitly use AFM. Aleksandrzak et al. discloses the use of multiple analytical techniques for characterizing graphitic nitride (g-C3N4) modified by rGO (see pg. 57: 2.1.4. for synthesis), such as AFM, TEM, XRD, FT-IR among others to characterize the graphitic nanomaterials (pg. 56: abstract). Aleksandrzak et al. specifically indicates that AFM is useful for determining the number of layers stacked to make the g-C3N4-rGO composite and also to characterize the topology the composite (pg. 57-58: 3. Results and Discussion) as rGO and the composite have different sizes lengths and flatness.
Since Zhang et al. and Aleksandrzak et al. are directed toward g-C3N4-rGO-based composites, applying all of the analytical methods would be obvious to one of ordinary skill in the art. Prior to the effective filing date of the claimed invention, the skilled artisan could reasonably be expected to use AFM measurements as indicated by Aleksandrzak et al. on the Ru-modified g-C3N4-rGO catalyst of Zhang et al. with the reasonable expectation of being able to characterize said composite to confirm the formation of C3N4-rGO nanosheets.
10. Claims 4, 5, 14, and 15 are rejected under 35 U.S.C. 103 as being unpatentable over Zhang et al. in view of Lee et al. as applied to Claims 3 (for Claims 4 and 5) and 13 (for Claims 14 and 15) above, and further in view of Du et al. with evidentiary support from Mahmood et al.
Zhang et al. (“Fabrication of Novel Ternary Three-Dimensional RuO2/Graphitic-C3N4@reduced Graphene Oxide Aerogel Composites for Supercapacitors,” ACS Sustainable Chem. Eng. 2017, 5(6), 4982-4991 and supporting information) is directed toward a 3D ternary composite (pg. 4982: title and abstract). Lee et al. (“Hydrous RuO2 nanoparticles as highly active electrocatalysts for hydrogen evolution reaction,” Chem. Phys. Lett. 2017, 673, 89-92) is directed toward ruthenium oxide nanoparticles for HER (pg. 89: title and abstract). Du et al. (“Facile synthesis of monodisperse ruthenium nanoparticles supported on graphene for hydrogen generation from hydrolysis of ammonia borane,” Int. J. Hydrogen Ener. 2015, 40, 6180-6187) is directed toward ruthenium nanoparticles (pg. 6180: title and abstract). Mahmood et al. (“An efficient and pH-universal ruthenium-based catalyst for hydrogen evolution reaction,” Nature Nanotech. 2017, 12, 441-447) is directed at a Ru-catalyst for HER (pg. 441: abstract).
Regarding Claim 4, Zhang et al. in view of Lee et al. discloses the device of Claim 3 where the active material (i.e.: the HER catalyst) is ruthenium oxide. However, ruthenium is known to have multiple oxidation states including Ru(0), Ru(II), Ru(III), and Ru(IV) as a result various ruthenium species, such as Ru nanoparticles, can be used to access the HER catalytic cycle (Mahmood pg. 443-444). Mahmood further explains using DFT calculations that the Ru-H formed on the Ru55 surface as well as the strong attraction of H2O to the nanoparticle surface (Mahmood pg. 444) are crucial for HER catalysis. Mahmood further provides evidence of inherency of the HER catalytic ability of Ru nanoparticles on a graphitic surface (formed from the reduction of RuCl3) on pg. 444 in Figure 3 and pg. 445 in Figure 4.
Du et al. is also directed toward the synthesis of Ru nanoparticles on a reduced graphene oxide matrix via the ascorbic acid mediated reduction of RuCl3 and graphene oxide (pg. 6181: Synthesis of Ru/graphene catalysts). Complete reduction of the graphene oxide by ascorbic acid was confirmed by Raman spectroscopy as illustrated in Fig. 2 and explained on pg. 6183 of Du et al. where Raman analysis indicates shows the complete graphitization of GO by the intensity ratio of ID to IG peaks (meaning GO is no longer present). This procedure of the in-situ reduction of RuCl3 and graphene oxide results in monodisperse Ru-NP well dispersed across the surface of rGO (Fig. 1a – TEM image in Du et al.). A lack of agglomeration and uniform particle size will result in efficient catalysis.
It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify the electrode in the device of Zhang et al. and Lee et al. by using the in-situ ascorbic acid reduction of RuCl3 and graphene oxide as taught by Du et al. with the reasonable expectation of forming an active HER catalyst (i.e.: predictable results given the use of Ru-NPs).
Therefore, the limitation “wherein the reducing includes ascorbic acid” in Claim 4 has been met.
Regarding Claim 5, Zhang et al. in view of Lee et al. discloses the device of Claim 3 where the active material (i.e.: the HER catalyst) is ruthenium oxide. However, ruthenium is known to have multiple oxidation states including Ru(0), Ru(II), Ru(III), and Ru(IV) as a result various ruthenium species, such as Ru nanoparticles, can be used to access the HER catalytic cycle (Mahmood pg. 443-444). Mahmood further explains using DFT calculations that the Ru-H formed on the Ru55 surface as well as the strong attraction of H2O to the nanoparticle surface (Mahmood pg. 444) are crucial for HER catalysis. Mahmood further provides evidence of inherency of the HER catalytic ability of Ru nanoparticles on a graphitic surface (formed from the reduction of RuCl3) on pg. 444 in Figure 3 and pg. 445 in Figure 4.
Du et al. is also directed toward the synthesis of Ru nanoparticles on a reduced graphene oxide matrix via the ascorbic acid mediated reduction of RuCl3 and graphene oxide (pg. 6181: Synthesis of Ru/graphene catalysts). Complete reduction of the graphene oxide by ascorbic acid was confirmed by Raman spectroscopy as illustrated in Fig. 2 and explained on pg. 6183 of Du et al. where Raman analysis indicates shows the complete graphitization of GO by the intensity ratio of ID to IG peaks (meaning GO is no longer present). This procedure of the in-situ reduction of RuCl3 and graphene oxide results in monodisperse Ru-NP well dispersed across the surface of rGO (Fig. 1a – TEM image in Du et al.). A lack of agglomeration and uniform particle size will result in efficient catalysis.
It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify the electrode in the device of Zhang et al. and Lee et al. by using the in-situ ascorbic acid reduction of RuCl3 and graphene oxide as taught by Du et al. with the reasonable expectation of forming an active HER catalyst (i.e.: predictable results given the use of Ru-NPs).
Therefore, the limitation “wherein the incorporation includes refluxing reducing includes ascorbic acid” in Claim 5 has been met.
Regarding Claim 14, Zhang et al. in view of Lee et al. discloses the catalytic material of Claim 13 where the active material (i.e.: the HER catalyst) is ruthenium oxide. However, ruthenium is known to have multiple oxidation states including Ru(0), Ru(II), Ru(III), and Ru(IV) as a result various ruthenium species, such as Ru nanoparticles, can be used to access the HER catalytic cycle (Mahmood pg. 443-444). Mahmood further explains using DFT calculations that the Ru-H formed on the Ru55 surface as well as the strong attraction of H2O to the nanoparticle surface (Mahmood pg. 444) are crucial for HER catalysis. Mahmood further provides evidence of inherency of the HER catalytic ability of Ru nanoparticles on a graphitic surface (formed from the reduction of RuCl3) on pg. 444 in Figure 3 and pg. 445 in Figure 4.
Du et al. is also directed toward the synthesis of Ru nanoparticles on a reduced graphene oxide matrix via the ascorbic acid mediated reduction of RuCl3 and graphene oxide (pg. 6181: Synthesis of Ru/graphene catalysts). Complete reduction of the graphene oxide by ascorbic acid was confirmed by Raman spectroscopy as illustrated in Fig. 2 and explained on pg. 6183 of Du et al. where Raman analysis indicates shows the complete graphitization of GO by the intensity ratio of ID to IG peaks (meaning GO is no longer present). This procedure of the in-situ reduction of RuCl3 and graphene oxide results in monodisperse Ru-NP well dispersed across the surface of rGO (Fig. 1a – TEM image in Du et al.). A lack of agglomeration and uniform particle size will result in efficient catalysis.
It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify the electrode in the device of Zhang et al. and Lee et al. by using the in-situ ascorbic acid reduction of RuCl3 and graphene oxide as taught by Du et al. with the reasonable expectation of forming an active HER catalyst (i.e.: predictable results given the use of Ru-NPs).
Therefore, the limitation “wherein the reducing includes ascorbic acid” in Claim 14 has been met.
Regarding Claim 15, Zhang et al. in view of Lee et al. discloses the catalytic material of Claim 13 where the active material (i.e.: the HER catalyst) is ruthenium oxide. However, ruthenium is known to have multiple oxidation states including Ru(0), Ru(II), Ru(III), and Ru(IV) as a result various ruthenium species, such as Ru nanoparticles, can be used to access the HER catalytic cycle (Mahmood pg. 443-444). Mahmood further explains using DFT calculations that the Ru-H formed on the Ru55 surface as well as the strong attraction of H2O to the nanoparticle surface (Mahmood pg. 444) are crucial for HER catalysis. Mahmood further provides evidence of inherency of the HER catalytic ability of Ru nanoparticles on a graphitic surface (formed from the reduction of RuCl3) on pg. 444 in Figure 3 and pg. 445 in Figure 4.
Du et al. is also directed toward the synthesis of Ru nanoparticles on a reduced graphene oxide matrix via the ascorbic acid mediated reduction of RuCl3 and graphene oxide (pg. 6181: Synthesis of Ru/graphene catalysts). Complete reduction of the graphene oxide by ascorbic acid was confirmed by Raman spectroscopy as illustrated in Fig. 2 and explained on pg. 6183 of Du et al. where Raman analysis indicates shows the complete graphitization of GO by the intensity ratio of ID to IG peaks (meaning GO is no longer present). This procedure of the in-situ reduction of RuCl3 and graphene oxide results in monodisperse Ru-NP well dispersed across the surface of rGO (Fig. 1a – TEM image in Du et al.). A lack of agglomeration and uniform particle size will result in efficient catalysis.
It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to modify the electrode in the device of Zhang et al. and Lee et al. by using the in-situ ascorbic acid reduction of RuCl3 and graphene oxide as taught by Du et al. with the reasonable expectation of forming an active HER catalyst (i.e.: predictable results given the use of Ru-NPs).
Therefore, the limitation “wherein the incorporation includes refluxing reducing includes ascorbic acid” in Claim 15.
Conclusion
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/KEVIN SYLVESTER/Examiner, Art Unit 1794
/JAMES LIN/Supervisory Patent Examiner, Art Unit 1794