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 .
Drawings
2. A new corrected drawing in compliance with 37 CFR 1.121(d) is required in this application for FIG. 4 because the correlation between the legend and bars in the graph are unclear as the two patterns (for CO and H2) are too similar to be easily distinguished in the grainy photocopy. The examiner is proposing using hashed lines of two different orientations (e.g.: horizonal and vertical patterns or a solid colored and a hashed patterns) to correct FIG. 4. Applicant is advised to employ the services of a competent patent draftsperson outside the Office, as the U.S. Patent and Trademark Office no longer prepares new drawings. The corrected drawings are required in reply to the Office action to avoid abandonment of the application. The requirement for corrected drawings will not be held in abeyance.
Claim Rejections - 35 USC § 102
3. 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.
4. Claims 1, 2, 3, and 4 are rejected under 35 U.S.C. 102(a)(1) as anticipated Goyal et al.
Goyal et al. (“Effect of monometallic copper on zeolitic imidazolate framework-8 synthesized by hydrothermal method,” J. Phys.: Conf. Ser. 2018, 1123, article 012062, pg. 1-6) is directed toward doping ZIF-8 (pg. 1: title)
Regarding Claim 1, Goyal et al. discloses a catalyst/material capable of carbon dioxide reduction as supported by a copper-based ZIF that catalyzes the photoconversion of CO2 to methanol (pg. 1: introduction). Goyal et al. further indicates that catalyst is modified ZIF-8 which is doped with copper (pg. 1: abstract). Copper is doped into a ZIF-based compound which has a structure where Zn and imidazole-based organic material are bound together (pg. 2: Synthesis Cu/ZIF-8). Support for the ZIF-based structure in which Zn is bound to 2-methylimidazole is the similarity of the crystal structures between pristine ZIF-8 and Cu-doped ZIF-8 as illustrated in Figure 1a and Figure 1b (pg. 3).
Regarding Claim 2, Goyal et al. discloses the CO2 reduction catalyst of Claim 1 where the Cu-doped ZIF-8 is prepared by the addition of 0.5 g copper(II) nitrate trihydrate (MW = 241.60 g/mol, 2.07 mmol Cu) to 0.25 g ZIF-8 (C8H10N4Zn, MW = 227.58 g/mol, 1.10 mmol) on pg. 2 in the synthesis section. Using the ratio of Cu to Zn in the synthesis, the maximum molar ratio of moles of Cu to total moles of metal (i.e.: Zn + Cu) is ~65 mol%, but the EDS spectrum in Figure 1c suggests that the more Zn than Cu is present in Cu-doped ZIF-8. Therefore, Goyal suggests that the ratio of moles of Cu to the total moles of Cu+Zn falls within the claimed range, thus resulting in a prima facie case of anticipation. See MPEP 2131.03(I).
Regarding Claim 3, Goyal et al. discloses the CO2 reduction catalyst of Claim 1, wherein the imidazole-based organic material is 2-methylimidzaole as evidenced on pg. 2 in the synthesis section.
Regarding Claim 4, Goyal et al. discloses the carbon dioxide catalyst of Claim 1, wherein the modified ZIF-based compound and a nitrogen atom of the imidazole-based organic material form a coordination bond with Zn or Cu as supported by the image of the nanocrystals of the Cu-doped ZIF material in Figure 1b, which is similar to other ZIF-based structure in which Zn is bound to 2-methylimidazole (pg. 3). In the pristine ZIF compound, Zn is bound to the 2-methylmidazole via the nitrogen.
5. Claims 1, 2, 3, and 4 are rejected under 35 U.S.C. 102(a)(1) as anticipated Wei et al.
Wei et al. (CN111454462A – EPO translation) is directed toward a Zn-Cu-ZIF bimetallic MOF (title).
Regarding Claim 1, Wei et al. discloses a catalyst/material for carbon dioxide reduction as supported Ex. 1, Ex. 2., and Ex. 3 (¶25-34) where the catalyst is a copper-doped ZIF. Wei et al. further discloses the bimetallic catalyst is generally prepared from a mixture of copper(II) nitrate, zinc nitrate, and benzimidazole ¶8. The Cu-doped ZIF-based compound (ZIF-8) converts CO2 to CO and hydrogen (¶27). Support for Zn being bound to the imidazole is found in ¶31 and supported by Figure 1 which shows the Cu-doped ZIF has a a similar XRD pattern to the pristine ZIF (i.e.: copper-free).
Regarding Claim 2, Wei et al. discloses the carbon dioxide catalyst of Claim 1, wherein the Cu doping amount was 5 mol% Cu (Ex. 1), 10 mol% Cu (Ex. 2), and 30 mol% Cu (Ex. 3) in ¶25-34. Wang et al. indicated that CO2 was converted to CO at all copper doping levels with lower doping levels having slightly better selectivity and activity (¶27, ¶30, and ¶34). A prima facie case of obviousness exists when the prior art discloses example(s) that fall within the claims range. See MPEP 2131.03(I).
Regarding Claim 3, Wei et al. discloses the carbon dioxide catalyst of Claim 1, wherein the imidazole-based organic material is benzimidazole as evidenced by Ex. 1, Ex. 2, and Ex.3 used to make copper-doped ZIFs (¶25-34).
Regarding Claim 4, Wei et al. discloses the carbon dioxide catalyst of Claim 1, wherein the modified ZIF-based compound and a nitrogen atom of the imidazole-based organic material form a coordination bond with Zn or Cu as supported by Figure 1 which shows the Cu-doped ZIF has a similar XRD pattern to the pristine ZIF (i.e.: copper-free). In the pristine ZIF compound, Zn is bound to benzimidazole via the nitrogen.
Claim Rejections - 35 USC § 103
6. 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.
7. Claims 5 and 6 are rejected under 35 U.S.C. 103 as being unpatentable over Goyal et al. as applied to Claim 1 above, and further in view of Wang et al.
Goyal et al. (“Effect of monometallic copper on zeolitic imidazolate framework-8 synthesized by hydrothermal method,” J. Phys.: Conf. Ser. 2018, 1123, article 012062, pg. 1-6) is directed toward doping ZIF-8 (pg. 1: title). Wang et al. (“Zinc Imidazolate Metal–Organic Frameworks (ZIF-8) for Electrochemical Reduction of CO2 to CO,” ChemPhysChem 2017, 18, 3142-3147) is directed toward a ZIF catalyst that reduces CO2 (pg. 3142: title).
Regarding Claim 5, Goyal et al. discloses the CO2 reduction catalyst of Claim 1. Goyal et al. indicates that the Cu-doped ZIF-8 material is thermally more stable than the pristine ZIF-8 as supported by the discussion on pg. 4 and Figure 3. UV-Vis analysis of the Cu-doped ZIF revealed that this material has a smaller bandgap than the pristine ZIF-8 and further would support more facile electron movement (in either electrochemical or photochemical promoted reactions) according to pg. 4 (Figure 4). However, Goyal et al. does not provide any specific details around the catalyst of Claim 1 as used in an electrode.
Wang et al. is directed toward a ZIF-8 based for the electrochemical reduction of CO2 (pg. 3142: title and abstract). Wang et al. further indicates that the reduction products of CO2 include hydrogen gas and carbon monoxide (pg. 3142-3145 and Figure 4 and Figure 5). Both Wang et al. and Goyal et al. disclose ZIF-8 (i.e.: Zn) materials that have activity toward CO2 reduction meaning both references fall in the same field of art.
It would be obvious to one of ordinary skill in the art prior to the effective filing date of the claimed invention to use the Cu-doped ZIF catalyst taught by Goyal et al. in the electrode of Wang et al. (i.e.: pristine ZIF-catalyst on glassy carbon) with the reasonable expectation of forming an electrode with greater CO2 reduction activity since the Cu-based ZIF is known to have a lower bandgap which reduced the energetic barrier for electron transfer.
Regarding Claim 6, the combination of Goyal et al. and Wang et al. disclose the carbon dioxide reduction electrode of Claim 5, wherein the CO2 reduction electrode is one in which the carbon dioxide reduction catalyst is supported on a porous carbon support as evidenced by the use of glassy carbon electrodes for the CO2 reduction experiments (pg. 3142: introduction and experimental section on pg. 3145-3146).
Conclusion
8. The prior art made of record and not relied upon is considered pertinent to applicant's disclosure. Schejn et al. (“Cu2+-doped zeolitic imidazolate frameworks (ZIF-8): efficient and stable catalysts for cycloadditions and condensation reactions,” Catal. Sci. Technol. 2015, 5, 1829-1839) is directed toward copper doping of ZIF-8 (pg. 1829: title). Li et al. (CN109746022A – abstract only) is directed toward a highly dispersed copper-zinc catalyst for CO2 reduction (abstract).
10. Any inquiry concerning this communication or earlier communications from the examiner should be directed to KEVIN SYLVESTER whose telephone number is (703)756-5536. The examiner can normally be reached Mon - Fri 8:15 AM to 4:30 PM EST.
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If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, James Lin can be reached at 571-272-8902. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/KEVIN SYLVESTER/Examiner, Art Unit 1794
/JAMES LIN/Supervisory Patent Examiner, Art Unit 1794