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 § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or non-obviousness.
Claims 1 and 2 are rejected under 35 U.S.C. 103 as being unpatentable over Zhao (“Recent advance on engineering titanium dioxide nanotubes for photochemical and photoelectrochemical water splitting”; pages 728-744; Nano Energy – 2016) in view of Shaddad (“Cooperative catalytic effect of ZrO2 and α-Fe2O3 nanoparticles on BiVO4 photoanodes for enhanced photoelectrochemical water splitting”; pages 1-6; 2016).
Regarding claim 1, Zhao discloses a method of making a photoanode (abstract; pages 732-733, sections 3.1.3 to 3.2.3), the method comprising:
providing titanium nanotube arrays on a titanium substrate/titanium foil (page 729, col. 2, last paragraph; page 732, col. 1, section 3.1.3; page 735, col. 1, second paragraph); and
wherein the photoanode comprises a titanium substrate having TiO2 nanotubes (TNTs) uniformly distributed thereon using electrochemical deposition (the TNTs are deposited to titanium foil; page 729, col. 2, last paragraph; page 731, section 3.1.2; page 732, section 3.1.3; page 742, col. 1, first paragraph); and
wherein the titanium nanotubes can be doped with a semiconductor, i.e. WO3, to improve the efficiency of the photoanode (page 733, sections 3.2.3; page 736, col. 2, paragraph 2; page 737, col. 1, first paragraph; page 740, col. 2, first paragraph; page 741, col. 1, paragraphs 1-2).
Zhao fails to teach doping the TiO2 nanotubes with zirconium oxide (ZrO2) and iron oxide (Fe2O3) films.
Shaddad teaches a process of making a photoanode comprising a step of doping TiO2 surfaces with semiconductors, such as WO3, ZrO2 and Fe2O3, by an electrolytic synthesis deposition method. It was found that doping with ZrO2 and Fe2O3, which mainly act as catalysts, remarkably enhanced water oxidation kinetics of the photoanodes, in photoelectrochemical water splitting operations, to carry out hydrogen and oxygen evolution reactions (abstract; page 2; page 4, col. 1, second paragraph; page 5, col. 1, paragraphs 1-3).
The photoanode of Zhao is also used in photoelectrochemical water splitting devices for hydrogen production using semiconductor materials (abstract; page 729, col. 1, paragraphs 1-2).
Therefore, it would have been obvious to one having ordinary skill in the art at the time of filing to dope the nanotubes of Zhao with zirconium oxide (ZrO2) and iron oxide (Fe2O3) films, because as taught by Shaddad, these catalysts remarkably enhance water oxidation kinetics of photoanodes to carry out hydrogen and oxygen evolution reactions in photoelectrochemical devices, and one would have a reasonable expectation of success in doing so.
Regarding claim 2, Zhao further discloses wherein the titanium nanotube arrays are provided on the titanium substrate by subjecting the titanium substrate to two rounds of electrochemical anodization (page 729, col. 2, last paragraph; page 732, col. 1, section 3.1.3).
Claims 3-5 are rejected under 35 U.S.C. 103 as being unpatentable over Zhao in view of Shaddad as applied to claim 1 above, and further in view of Pontes Bittencourt Quitete et al. (US Patent Application Publication no. 2023/0059034 – referred to as Pontes hereinafter).
Regarding claim 3, Zhao in view of Shaddad teaches all the features discussed above, but fails to disclose wherein the electrochemical deposition comprises using an electroplating solution including ZrCl2O.8H2O and FeCl2 for doping the titanium nanotubes.
Pontes teaches a method for preparing a catalyst made up of iron and zirconium using a solution containing a soluble salt or iron (i.e. FeCl2) and a soluble salt of zirconium, such as zirconium oxychloride octahydrate (ZrCl2O.8H2O – paragraph 30).
One having ordinary skill in the art at the time of filing would have found it obvious to use a solution including ZrCl2O.8H2O and FeCl2 in the method of the modified Zhao because as taught by Pontes, this is well known in the art to be effective for preparing catalysts made up of zirconium and iron for water electrolytic operations, and one would have a reasonable expectation of success in doing so.
Regarding claim 4, Pontes teaches a method for preparing a catalyst made up of iron and zirconium using a solution containing a soluble salt of iron (i.e. FeCl2) and a soluble salt of zirconium, such as zirconium oxychloride octahydrate (ZrCl2O.8H2O – paragraph 30), but fails to teach wherein the electroplating solution contains about 20 mM FeCl2 and an amount of ZrCl2O.8H2O in a Zr/Fe molar ratio of about 1.5 to about 6.5%.
Shaddad further discloses that best performance was obtained for 2.5 mole % zirconium, and wherein the efficiency is remarkably enhanced by Zr and Fe additions compared with other materials (page 2, col. 1, last paragraph, figure 1). Therefore, one having ordinary skill in the art at the time of filing would have found it obvious to determine the optimum Zr/Fe molar ratio and concentration of FeCl2 in the electroplating solution of the modified Zhao by routine experimentation. It has been held by courts that generally, differences in concentration not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. Where the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation." In reAller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). MPEP 2144.05.II.A.
Regarding claim 5, Shaddad teaches that best performance was obtained for 2.5 mole % zirconium, and wherein the efficiency is remarkably enhanced by Zr and Fe additions compared with other materials (page 2, col. 1, last paragraph). Therefore, one having ordinary skill in the art at the time of filing would have found it obvious to determine the optimum Zr/Fe molar ratio in the electroplating solution of the modified Zhao by routine experimentation. It has been held by courts that generally, differences in concentration not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. Where the general conditions of a claim are disclosed in the prior art, it is not inventive to discover the optimum or workable ranges by routine experimentation. In reAller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). MPEP 2144.05.II.A.
Response to Arguments
Applicant's arguments filed on March 23, 2026 have been fully considered but they are not persuasive. The applicant argues that Shaddad is silent with respect to modification of titanium, and thus there is no teaching or suggestion that the dopants of Shaddad or the doping methods of Shaddad would be effective when doping TiO2 nanoparticles. Shaddad teaches an incompatible method that includes sequential electrolytic deposition. Zhao in view of Shaddad fails to teach doping the titanium nanotubes with zirconium oxide and iron oxide films using electrochemical deposition to provide the photoanode.
In response to applicant’s argument that there is no teaching, suggestion, or motivation to combine the references, the examiner recognizes that obviousness may be established by combining or modifying the teachings of the prior art to produce the claimed invention where there is some teaching, suggestion, or motivation to do so found either in the references themselves or in the knowledge generally available to one of ordinary skill in the art. See In re Fine, 837 F.2d 1071, 5 USPQ2d 1596 (Fed. Cir. 1988), In re Jones, 958 F.2d 347, 21 USPQ2d 1941 (Fed. Cir. 1992), and KSR International Co. v. Teleflex, Inc., 550 U.S. 398, 82 USPQ2d 1385 (2007).
In this case, the disclosures of Zhao and Shaddad are both related to methods for improving photoanodes for water splitting operations. Zhao teaches doping pre-formed TiO2 nanotubes with WO₃. The teachings of Shaddad were provided to show that doping with ZrO₂ and Fe₂O₃, by an electrolytic synthesis deposition method, represents an improvement of photoanodes over doping with WO₃. Even though Shaddad discusses specifics for only BiVO₄, Shaddad also discloses that this would be applicable to other photoelectrode materials, including TiO2 (page 1, col. 2, second paragraph; page 4, col. 1, second paragraph). One having ordinary skill in the art would have found it obvious to electrodeposit ZrO₂ and Fe₂O₃ on TiO2 photoanodes, as suggested by Shaddad, in order to enhance water oxidation kinetics of the WO3-doped photoanodes of Zhao with a reasonable expectation of success in doing so.
In response to applicant's argument that the examiner's conclusion of obviousness is based upon improper hindsight reasoning, it must be recognized that any judgment on obviousness is in a sense necessarily a reconstruction based upon hindsight reasoning. But so long as it takes into account only knowledge which was within the level of ordinary skill at the time the claimed invention was made, and does not include knowledge gleaned only from the applicant's disclosure, such a reconstruction is proper. See In re McLaughlin, 443 F.2d 1392, 170 USPQ 209 (CCPA 1971).
The Examiner notes that the claims do not preclude “sequential electrolytic deposition” by virtue of the "comprising" transitional phrase. The previous rejections in view of Zhao and Shaddad are still deemed proper and are maintained.
Conclusion
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ZULMARIAM MENDEZ whose telephone number is (571)272-9805. The examiner can normally be reached M-F 8am-4:30p.
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/ZULMARIAM MENDEZ/Primary Examiner, Art Unit 1794
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