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 .
Election/Restrictions
Applicant’s election without traverse of the materials as required in claim 12 and preparing the separation layer by electrochemical deposition in the reply filed on 6/5/2026 is acknowledged.
Claims 3, 5, 9-11, and 13 are withdrawn from further consideration pursuant to 37 CFR 1.142(b) as being drawn to a nonelected species, there being no allowable generic or linking claim. Election was made without traverse in the reply filed on 6/5/2026.
Specification
The abstract of the disclosure is objected to because it exceeds 150 words. A corrected abstract of the disclosure is required and must be presented on a separate sheet, apart from any other text. See MPEP § 608.01(b).
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claim 7 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Regarding claim 7, the claim states that the hollow base membrane is characterized in that it has an inner diameter of 1.2~1.7 microns and an outer diameter of 2~3 microns, however, the figures suggest that the inner and outer diameter of the fiber is much larger than what is claimed, making it unclear whether the units in the claim are correct. Paragraphs 0051, 0053, and 0055 of the instant specification indicate that the membrane filament has an outer diameter of 2.5 mm and an inner diameter of 1.3 mm, which correlate better with the figures. Therefore, the claim is being interpreted as though the inner diameter of the hollow base membrane is 1.2 to 1.7 mm and the outer diameter of the hollow base membrane is 2 to 3 mm. Appropriate action is required without adding new matter.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
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.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claims 1, 2, 4, 6, 12, and 14 are rejected under 35 U.S.C. 103 as being unpatentable over Rabiee, “Tuning the Product Selectivity of the Cu Hollow Fiber Gas Diffusion Electrode for Efficient CO2 Reduction to Formate by Controlled Surface Sn Electrodeposition”, 2020 in view of Tan, CN 105195030 A, Liu, CN 110935328 A, Perera, US 2009/0305871 A1, and Koros, US 2017/0189866 A1.
The following citations for Tan and Liu are in reference to the machine
translations provided by Espacenet.
Regarding claim 1, Rabiee teaches synthesizing an asymmetric porous Cu hollow fiber gas diffusion electrode (HFGDE) with controlled Sn surface electrodeposition (abstract). They teach preparing the HFGDE via a dry-wet spinning process where the Cu powder was used as the inorganic precursor (pg. 21671, section 2.1). They teach that Cu was added to NMP as the solvent for phase inversion and then mixed with polyethersulfone as the polymer binder (pg. 61671, section 2.1). They teach that the solution was stirred at 60°C for 6 hours followed by stirring overnight to ensure that the solution was homogeneous (pg. 21671, section 2.1). They teach that the precursor was vacuumed for 1 h to remove bubbles before spinning through a stainless-steel vessel at room temperature (pg. 61671, section 2.1). They teach that the precursor was pumped through a spinneret rig to a nonsolvent bath (water), and deionized water was pumped through the bore of the spinneret (pg. 61671, section 2.1). They teach that the hollow fibers were kept in the nonsolvent bath overnight to finish phase inversion and remove NMP from the hollow fiber structure followed by drying at room temperature (pg. 61671, section 2.1). They teach that the green hollow fibers were calcined in an air atmosphere at 650°C for 2 h to remove the polymer and induce particle sintering followed by reducing the fibers back to Cu by hydrogenation at 500°C for 1 h (pg. 21671, section 2.1). Therefore, Rabiee teaches adding an inorganic material (copper), a polymer (PES), in an organic solvent (NMP) to form a mixture, mixing for 6 hours and then overnight, vacuuming so as to provide a casting liquid solution, using deionized water as an internal coagulant (bore liquid), spinning the casting liquid solution by a spinneret into a nonsolvent bath (water), where the fibers were kept in the external coagulant (nonsolvent bath) overnight to finish phase inversion and remove NMP, and calcining the fibers at 650°C for 2 hours. They further teach loading Sn on the Cu HFGDE by electrochemical deposition (abstract and pg. 21671-21672, section 2.2), such that they form a separation layer on an outer surface of the hollow base membrane by using electrochemical deposition to obtain the hollow fiber inorganic membrane.
They do not teach including a polymer in the mixture.
Tan teaches a method of forming a metal nickel alloy hollow fiber membrane by dissolving a dispersant in an organic solvent, adding nickel and alloy powder, adding in an organic polymer binder and stirring to obtain a stable metal powder casting solution, (0002 and 0011). They teach that the dispersant is PVP and the organic polymer adhesive is one of polyethersulfone, etc. (0012). They teach vacuuming for 1-5 hours to degas the solution and then transferring it to a spinning equipment tank (0014). They teach that the casting solution enters a condensate through a spinning head where after solidification a hollow fiber membrane precursor is obtained (0014), such that the casting liquid solution will be spun to obtain a membrane filament. They teach that the internal condensate or coagulant is a solvent or a mixture of solvent and a non-solvent, where the non-solvent may be water (0017), such that the internal coagulant will include water. They teach that the solution enters the condensate or external coagulant through the spinning head at 20-80°C for solidification, where since it solidifies in an external coagulant it is considered to perform phase inversion (0014), where the external coagulant or condensate is water or ethanol (0016). They teach drying the hollow fiber membrane for 20-28 hours and heating to 600-800°C and for 1-2 hours to burn off organic matter followed by sintering to obtain a dense hollow fiber nickel alloy membrane (0020).
From the teachings of Tan, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have modified the process of Rabiee to have included PVP as a polymer dispersant in the mixture because Tan teaches that PVP is a desirable dispersant included in the mixture for forming a hollow fiber membrane using a metal along with PES and a solvent such that it will also be expected to help disperse the materials in the mixture. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have spun the fibers into the external coagulant at 20-80°C because Tan teaches that such a temperature is suitable for the solidification process and because Rabiee does not specify a temperature for the process, suggesting the room temperature is suitable which will be within the range suggested by Tan. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have dried the hollow membrane body for 20-28 hours followed by calcining at 600-800°C for 1-2 hours because Tan teaches that such a drying time and calcining temperature and time are desirable for forming a hollow fiber membrane using PES, a metal, and an additive such that it will be expected to provide a suitable drying time and calcining temperature/time for removing solvent and the polymer material in forming the copper hollow fiber membrane.
Therefore, the temperature of phase inversion and calcination overlaps the
claimed range, the time for drying overlaps the claimed range, and the time for calcination is within the claimed range. According to MPEP 2144.05, "in the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists." According to MPEP2131.03, "[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is "anticipated" if one of them is in the prior art."
They do not teach ball milling, vacuuming for the required time range, using tap
water as an internal coagulant, or performing phase inversion for the requirement time.
Liu teaches preparing an organic fluorinated polymer-doped perovskite hollow
fiber oxygen-permeable membrane (0002). They teach preparing the membrane by
mixing a raw material powder including a metal oxide, carbonate, and organic
fluoropolymer, with a polymer binder, dispersant, and organic solvent (0009-0010).
They teach ball milling the mixture to obtain a uniformly dispersed spinning solution,
where the ball milling is done for 12-28 hours (0010 and 0014). They teach that after
degassing, the spinning solution is spun and enters an external coagulation bath to
solidify and obtain a hollow fiber perform (0010). They teach drying the hollow fiber
preform and then successively pretreating in a low-temperature section, reacting and
sintering in a high-temperature section, and then cooling to obtain a fluorine-containing
perovskite hollow fiber oxygen-permeable membrane (0011). They teach that the
polymer binder is polyethersulfone, polysulfone, polyetherimide, polycellulose acetate,
the organic solvent is any one of N-methylpyrrolidone, N,N-dimethylacetamide, and
dimethyl sulfoxide (0015). They teach that the dispersant is either polyvinylpyrrolidone
or Arlacel P135 (0015). They teach that the inner core liquid and outer coagulation bath for spinning are one or a mixture of two or more of deionized water, tap water, ethanol,
methanol, etc. (0017). They teach that the temperature of the inner core liquid and the outer coagulation bath of spinning is 10-30°C (0017). They teach soaking in the external
coagulation bath for 6-24 hours (0019).
From the teachings of Liu, it would have been obvious to a person having
ordinary skill in the art before the effective filing date of the claimed invention to have
modified the process of Rabiee in view of Tan to have ball milled for 12-28 hours because Liu teaches that such a process provides a uniformly dispersed spinning solution such that it will also be expected to provide a uniformly dispersed spinning solution in the process of Rabiee in view of Tan. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have soaked the membrane body in the external coagulant for 6-24 hours because Liu teaches that such a time frame is desirable in forming a hollow fiber membrane in a process similar to that of Rabiee in view of Tan and because Rabiee teaches keeping the membrane in the nonsolvent bath overnight suggesting that a time similar to the range of Liu is suitable, where overnight would be expected to include 8-12 hours such that the range of Liu is expected to also be suitable for the process of Rabiee in view of Tan. Further, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used tap water as the internal coagulant because Liu teaches that that tap water can be used as an internal coagulant in a process similar to that of Rabiee in view of Tan including using the same binders, dispersants, and solvents and because Rabiee and Tan teach using water such that it will be expected to provide a suitable coagulant in the process.
Therefore, in the process of Rabiee in view of Tan and Liu the material will be ball milled for a time overlapping the claimed range, tap water will be used as an internal coagulant, and phase inversion will be carried out under a temperature overlapping the claimed range for a time overlapping the claimed range. According to MPEP 2144.05, "in the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists."
They do not teach vacuuming for 24-28 hours.
Perera teaches a hollow fiber membrane (abstract). They teach preparing one or
more spinning dopes by combining a solvent, polymer, and ceramic powder (0066).
They teach that the mixture is placed on a rotary pump for 2-4 days to degas and form a
uniform spinning dope (0066). They teach that the fibers are produced by spinning
using an appropriate spinneret followed by heat treatment (0067).
From the teachings of Perera, it would have been obvious to a person having
ordinary skill in the art before the effective filing date of the claimed invention to have
degassed the solution under vacuum for 2-4 days because Perera teaches that such a
time is used for degassing a spinning solution such that it will be expected to ensure to
remove the gas as desired. Therefore, the vacuuming time will overlap the claimed
range. According to MPEP 2144.05, "in the case where the claimed ranges "overlap or lie
inside ranges disclosed by the prior art" a prima facie case of obviousness exists."
Alternatively, it would have been obvious to a person having ordinary skill in the
art before the effective filing date of the claimed invention to have optimized the time
for vacuuming to be within the claimed range to ensure that the solution is fully
degassed. According to MPEP 2144.05 II A, "Generally, differences in concentration or
temperature will not support the patentability of subject matter encompassed by the
prior art unless there is evidence indicating such concentration or temperature is
critical. "[W]here 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
re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
They do not teach using a syringe pump.
Koros teaches metal organic framework/polymer mixed matrix fiber membranes
and metal organic framework/carbon molecular sieve mixed-matrix hollow fiber
membranes (abstract). They teach spinning the hollow fiber membranes by delivering
the sheath, dope, core dope, and bore fluid to the spinneret with controlled flow rates by
syringe pumps (0088-0086).
From the teachings of Koros, it would have been obvious to a person having
ordinary skill in the art before the effective filing date of the claimed invention to have
spun the fibers using a spinneret and delivering the solution to the spinneret using
syringe pumps because Koros teaches that such a method is suitable for spinning hollow
fiber membranes. Therefore, the fluid will be spun by a spinneret and a syringe pump.
Regarding claim 2, Rabiee in view of Tan, Liu, Perera, and Koros suggest the process of claim 1, using copper as the inorganic material, polyvinylpyrrolidone as the polymer (dispersant), polyethersulfone as the binder, and NMP as the solvent. Rabiee teaches that water is the external coagulant (pg. 21671, section 2.1).
Tan teaches that the external condensate is water or ethanol (0016), where as noted above they teach using PVP as the polymer, NMP as the solvent, and PES as the polymer (0012).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used ethanol as the external coagulant because Tan teaches that ethanol can be used as an external coagulant as an alternative to water when using the materials suggested to be used in the process of Rabiee in view of Tan, Liu, Perera, and Koros. Therefore, the materials meet the requirements of claim 2.
Regarding claims 4 and 12, Rabiee in view of Tan, Liu, Perera, and Koros suggest the process of claims 1 and 2, where, as discussed above for claims 1 and 2, they suggest using copper as the inorganic material, PVP as the polymer, PES as the binder, and NMP as the solvent. As discussed above, Tan provides the suggestion of calcining the fibers at 600-800°C for 1-2 hours so as to overlap the claimed ranges.
Tan teaches using N,N-dimethylacetamide or N-methylpyrrolidone as the solvent (0016), where as noted above they teach using PVP as the polymer and PES as the polymer (0012).
From this, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have used N,N-dimethylacetamide as the solvent as an alternative to NMP because Tan teaches that it is a suitable solvent for forming inorganic hollow fiber membranes using the materials of Rabiee in view of Tan, Liu, Perera, and Koros. Therefore, the solvent will be N,N-dimethylacetamide.
They do not teach mixing the materials at the claimed ratio. According to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here 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 re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the materials to be within the claimed range so as to provide a desirable copper hollow fiber through routine experimentation.
Regarding claims 6 and 14, Rabiee in view of Tan, Liu, Perera, and Koros suggest the process of claims 1 and 2. Rabiee teaches including the copper in an amount of 65 wt. % (pg. 21671, section 2.1).
Tan teaches forming the nickel hollow fibers using a casting solution includes 105-130g of metal powder, 10-20g of organic polymer binder, 30-50g of organic solvent, and 1-3g of additives, i.e., dispersant or PVP (0011-0013). Therefore, the solution includes a range at which the amount of metal powder is greater than 70 wt%, for example, having 130 g of metal, 10 g of binder, 30 g of solvent, and 1 g of PVP.
From the teachings of Tan, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed the fibers using a casting solution that includes 105-130g of copper powder, 10-20g of organic polymer binder, 30-50g of organic solvent, and 1-3g of additives, i.e., dispersant or PVP because Tan teaches that such a material range is suitable for forming hollow fiber membranes from polymers and metal powders such that it will be expected to provide a desirable range for the copper hollow fibers of Rabiee. Therefore, the solution includes a range having copper in an amount overlapping the claimed range.
Further, according to MPEP 2144.05 II A, “Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. “[W]here 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 re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955). Therefore, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the materials to be within the claimed range so as to provide a desirable copper hollow fiber through routine experimentation.
Claim 7 is rejected under 35 U.S.C. 103 as being unpatentable over Rabiee in view of Tan, Liu, Perera, and Koros as applied to claim 1 above, and further in view of Herczeg, US 2003/0141238 A1 and Kas, US 2019/0271089 A1.
Regarding claim 7, Rabiee in view of Tan, Liu, Perera, and Koros suggest the process of claim 1. Rabiee teaches that the pore size distribution was 1-3 microns before and after 30 and 120 s of Sn electrodeposition (pg. 21674, section 3.1 and Fig. 2e). The figure depicts the base membrane, i.e., the uncoated Cu HFGDE membrane as having a pore size ranging from about 1 micron to about 3 microns, i.e., about the same as the coated membranes (Fig. 2e). Therefore, the pore size of the membrane is considered to overlap the claimed range at the end point of be so close to the claimed range to render it obvious. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” Alternatively, according to MPEP 2144.05(I): Similarly, a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close.
As to the porosity, Rabiee teaches that the porosity of the uncoated membrane is about 50% or slightly above 50% (Fig. 2d). They teach that the tin deposition time affects gas permeance by possibly blocking pores, where gas permeance decreases with reduced porosity (pg. 21673, section 3.1 and Fig. 2d). They teach that it is desirable for the HFGDE to have a gas resistance as low as possible, where the porosity of PES after phase inversion helps the flow (pg. 21673, section 3.1). They teach that HFDGEs can enhance the CO2RR stability by self-tuning the gas/liquid pressures when the overall CO2RR rate changes since the pore structure/size and porosity of the HFGDEs can be modified during the dry-wet fabrication process (pg. 21679, section 3.2).
They do not teach a porosity within the claimed range.
Herczeg teaches porous asymmetric hollow polymer fiber membranes (abstract). They teach preparing a hollow fiber membrane by spinning dope comprising a first polymer, as solvent and a nonsolvent, in ratio sufficient to form a homogeneous solution or a colloidal dispersion; extruding the dope in the form of a hollow pre-fiber form a nozzle having a rotating inner or outer element, the pre-fiber having an inside surface and an outside surface; contacting the inside surface of the pre-fiber with a coagulating medium; and coagulating the pre-fiber from the inside surface to the outside surface to provide a hollow fiber membrane (0022). They teach that the spinning dope preferably comprises a first polymer and a second polymer, where the first polymer comprises a sulfone polymer and the second polymer is polyvinyl pyrrolidone (0023). They teach that the hollow fiber membranes are prepared by phase inversion (0024). They teach that PVP is typically used as a pore former and morphology enhancer and is substantially removed during the preparation of the membrane (0040). They teach that the concentration of the pore former influences the pore size and pore distribution in the final membrane (0043).
From the teachings of Rabiee and Herczeg, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have optimized the porosity of the membrane to be within the claimed range by controlling the PVP used as a pore former because Rabiee teaches that it is desirable to have good flow through the membrane, where porosity enables good flow and the subsequent tin coating reduces porosity and Herczeg indicates that the inclusion of PVP in a spinning dope can act as a pore former, where pore formers influences the pore size and distribution, such that by optimizing the concentration of PVP in the spinning dope it will also be expected to optimize the porosity of the resulting film so as to increase the gas flow after tin deposition.
They do not specifically teach the size of the fibers.
Kas teaches a metal hollow fiber electrode the comprises aggregated copper particles (abstract). They teach that the metal hollow fibers can typically have an inner diameter of 0.1-10 mm, such as 0.5-5 mm, or 0.7-3 mm and an outer diameter of 0.1-10 mm, such as 0.5-5 mm, or 0.7-3 mm (0012). They teach that the fibers are formed by spinning a mixture containing copper particles, polymer, and solvent and pressing it through a spinneret into a coagulation bath where non-solvent induced phase separation arrests the copper particles in the polymer matrix (0016). They teach that by adding a bore-liquid during spinning, a hollow fiber is obtained and a thermal treatment decomposes the polymer and sinters the copper particles together (0016). They teach mixing copper powder and NMP followed by stirring and ultrasonic treatment for 30 min (0041). Thy teach after adding PEI, the mixture was heated and kept at 50°C and 60°C for 30 minutes and 2 hours respectfully (0041). They teach that the solution cooled down by stirring overnight followed by degassing by applying vacuum for 90 min (0041). They teach that spinning was carried out at room temperature (21±3°C) using a spinneret into a coagulation bath containing tap water (0042). They teach that deionized water was pumped through the bore of the spinneret (0042). They teach that the fibers were kept in the coagulation bath for 1 day to remove traces of NMP, followed by drying for 1 day (0043). They teach that the green copper hollow fibers were thermally treated at 600°C for 3 hours to remove the PEI and sinter the copper particles (0043).
From the teachings of Kas, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have formed the hollow fibers to have an inner diameter in the range of 0.1-10 mm, such as 0.5-5 mm, or 0.7-3 mm and an outer diameter of 0.1-10 mm, such as 0.5-5 mm, or 0.7-3 mm so as to overlap the claimed range because Kas teaches that such a range is desirable for a copper hollow fiber electrode such that it will also be expected to provide a suitable size range for the electrode of Rabiee. According to MPEP 2144.05, “in the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists.” Therefore, the size range is considered to render the claimed range obvious as interpreted in the 112(b) rejection above.
Claim 8 is rejected under 35 U.S.C. 103 as being unpatentable over Rabiee in view of Tan, Liu, Perera, and Koros as applied to claim 1 above, and further in view of Zhang, “High-performance Photoelectrocatalytic Reduction of CO2 by the hydrophilic-hydrophobic composite Cu-SnO2/ZIF-8”, 2020 and Wei, R., et al., “Aqueously Cathodic Deposition of ZIF-8 Membranes for Superior Propylene/Propane Separation”, 2020.
Regarding claim 8, Rabiee in view of Tan, Liu, Perera, and Koros suggest the process of claim 1. Rabiee teaches using the electrode for CO2 electrochemical reduction reaction where the enhancement of formate production and the suppression of the hydrogen by-product were attributed to the optimized ratio of SnOx species on the electrode surface (abstract).
They do not teach depositing ZIF-8 on the membrane.
Zhang teaches that photoelectrocatalytic reduction of CO2 can solve energy shortages and environmental problems bus poor solubility and intense competition of the hydrogen evolution reaction restrict CO2 activation (abstract). They teach forming hydrophilic-hydrophobic CU-SnO2/ZIF-8 composite catalysts by compounding hydrophobic ZIF-8 with hydrophilic CU-SnO2 (abstract). They teach that gas-phase CO-2 was directly used to improve the activation efficiency of CO2 molecules and hydrogen evolution was inhibited (abstract). They teach that the ZIF-8 unique structure promoted electron transfer and Cu-SnO2 dispersion to provide additional active sites (abstract). They teach that ZIF-8 layers are introduced on the surface of photocatalysts to suppress the competitive HER and enhance the interaction between CO2 and the catalyst to improve the efficiency and selectivity of CO-2 reduction (pg. 2, section 1). They teach that ZIF-8 with zeolite-like structure has excellent CO2 adsorption performance, a considerable specific surface area, and abundant rich pyridine N (pg. 2, section 1).
From the teachings of Zhang, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have included a ZIF-8 layer on the membrane because Rabiee provides a Cu-Sn/SnO2 membrane for CO2 reduction and Zhang indicates that including ZIF-8 in a Cu-SnO2 structure improves the activation efficiency of CO2 molecules and inhibits hydrogen evolution, where ZIF-8 promotes electron transfer and provides additional active sites while suppressing the HER and enhancing interaction between CO2 and a catalyst to improve the efficiency and selectivity of CO2 reduction such that it will be expected to enhance the performance of the electrode.
They do not teach applying the ZIF-8 using the claimed method. As noted above they teach applying tin by electrodeposition.
Wei teaches aqueously cathodic deposition (ACD) to fabricate ZIF-8 type of MOF membranes (abstract). They teach that a low-defect density membrane is obtained with superior separation performance (abstract). They teach preparing a precursor solution for electrodeposition of ZIF-8 membranes by dissolving 2-methylimidazole (2-MIM) (4.105g, 50 mmole) in DI water (50 mL) (pg. 5, section 2.4 and pg. 6, section 4). In a separate container they dissolve zinc acetate dihydrate (0.183g, 0.83 mmol) in DI water (10 mL) (pg. 6, section 4). They teach mixing the solutions together and stirring for 5 s to form the ZIF-8 precursor solution for the cathodic deposition (pg. 6, section 4). They teach coating AAO substrates with Pt/Pd and separating the formed substrate from graphite paper by 1.5 cm and immersing in the ZIF-8 precursor solution (pg. 6, section 4). They teach performing the reaction for 10, 20, 30, 40, and 60 minutes under a current density of 0.13 mA/cm2 (pg. 6, section 4). They teach rinsing the membranes by DI water and methanol after the reaction (pg. 6, section 4). They teach that the coated AAO membrane was used as the working electrode on the cathode side and graphite paper was used as the counter electrode (anode) (pg. 2, section 2.1 and Fig. 1). They teach that the approach provides ultra-facile fabrication of MOF membranes on the substrate without addition of any supporting electrolyte or modulator to fabricate an ultrathin membrane consisting of a single layer of crystals with low-defect density (pg. 5, section 3).
From the teachings of Wei, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have provided the ZIF-8 coating using their ACD approach on the copper membrane because Rabiee teaches using electrodeposition for forming the tin layer, suggesting that such a method is suitable for applying material to the copper hollow fiber membrane and because Wei teaches that it provides ultra-facile fabrication of MOF membranes on the substrate without addition of any supporting electrolyte or modulator to fabricate an ultrathin membrane consisting of a single layer of crystals with low-defect density such that it will be expected to provide the ZIF-8 layer as desired. Further, since Wei teaches dissolving the materials in DI water, it would have been obvious to a person having ordinary skill in the art before the effective filing date of the claimed invention to have mixed the solutions uniformly so as to enhance or facilitate dissolving the materials. Therefore, they suggest forming the ZIF-8 layer using the claimed method, using material amounts and concentrations meeting the claimed ranges, and having the reaction proceed to for a time including 30 minutes so as to form the layer. According to MPEP 2131.03, “[W]hen, as by a recitation of ranges or otherwise, a claim covers several compositions, the claim is ‘anticipated’ if one of them is in the prior art.”
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to CHRISTINA D MCCLURE whose telephone number is (571)272-9761. The examiner can normally be reached Monday-Friday, 8:30-5:00 EST.
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/CHRISTINA D MCCLURE/ Examiner, Art Unit 1718
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