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 .
Response to Amendments
This is a final office action in response to applicant's arguments and remarks filed on 01/02/2026.
Status of Rejections
The objections to the claims are withdrawn in view of applicant’s amendments.
All previous rejections are withdrawn in view of applicant’s amendments.
New grounds of rejection are necessitated by applicant’s amendments.
Claims 1-12 are pending and under consideration for this Office Action.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claim 8 is rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends. Claim 8 recites the limitation of “covalent bonds are present at an interface between each nanoparticle of the plurality of nanoparticles and a respective conductive projection of the array of conductive projections”, and therefore fails to further limit claim 1, which already recites the limitation of “covalent nitride bonds…are present at an interface between each nanoparticle of the plurality of nanoparticles and a respective conductive projection of the array of conductive projections” in lines 15-18. Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
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 and 10-12 are rejected under 35 U.S.C. 103 as being unpatentable over Wei et al. (“Photoelectrocatalytic reduction of CO2 to syngas over Ag nanoparticle modified p-Si nanowire array” and Supplementary Information, Nanoscale, May 2019) in view of Luc et al. (“Ag–Sn Bimetallic Catalyst with a Core–Shell Structure for CO2 Reduction”, J. Am. Chem. Soc., 2017), and further in view of Zhang et al. (“Ultrasmall MoOx Clusters as a Novel Cocatalyst for Photocatalytic Hydrogen Evolution”, Adv. Mater., 2018), Vanka et al. (“High Efficiency Si Photocathode Protected by Multifunctional GaN Nanostructures”, Nano Lett., 2018), and Cui et al. (“GaN nanowire field emitters with the adsorption of Pt nanoparticles”, RSC Adv., 2017).
Regarding claim 1, Wei teaches an electrode of a chemical cell (see e.g. Page 12531, Col. 1, bottom paragraph, lines 1-3, working photocathode in cell for reduction), the electrode comprising:
a substrate having a surface (see e.g. Fig. 1a, Si wafer base);
an array of conductive projections supported by the substrate and extending outward from the surface of the substrate, each conductive projection of the array of conductive projections having a semiconductor composition for catalytic conversion of carbon dioxide (CO2) in the chemical cell (see e.g. Fig. 1a, array of Si nanowires for photoelectrocatalytic reduction of CO2 extending up from Si base; Page 12531, Col. 1, lines 6-8); and
a plurality of nanoparticles disposed over the array of conductive projections, each nanoparticle of the plurality of nanoparticles having a metallic composition for the catalytic conversion of carbon dioxide (CO2) in the chemical cell (see e.g. Fig. 1a, Ag nanoparticles for photoelectrocatalytic reduction of CO2 loaded on the Si nanowire array; Page 12531, Col. 1, lines 6-8);
wherein each nanoparticle of the plurality of nanoparticles has a size at least an order of magnitude smaller than a lateral dimension of each conductive projection of the array of conductive projections (see e.g. Fig. 2, Page 12531, Col. 1, under “Results and discussion”, line 10, and Col. 2, bottom paragraph, lines 2-3, Ag NPs with average sizes from 4.2 to 16 nm on Si NWs with diameter of ~150 nm, i.e. at least an order of magnitude greater).
Wei does not teach the metallic composition comprising a core and an outer layer surrounding the core, the core comprising a metal, and the outer layer comprising a metal oxide of the metal. Wei does however teach the metallic composition comprising Ag (see Fig. 1a, Ag NPs).
Luc teaches an electrocatalyst for CO2 reduction (see e.g. Abstract) comprising nanoparticles including an Ag-Sn bimetallic core with a SnOx outer shell (see e.g. Scheme 1 and Page 1886, lines 13-20), this core-shell nanostructure providing high electrical conductivity from the core and tailored high electrocatalytic activity from the shell (see e.g. Page 1886, Col. 1, lines 13-7) and enabling high performance conversion of CO2 to value-added formate (see e.g. Page 1885, Cl. 1, lines 1-4, and Page 1891, under “CONCLUSION”, lines 1-4).
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 metallic composition of Wei to comprise an Ag-Sn bimetallic core with a SnOx outer shell as taught by Luc as an alternate suitable Ag-comprising nanoparticle composition of CO2 reduction that provides high electrical conductivity and electrocatalytic activity while enabling high performance conversion of the CO2 to value-added formate. MPEP § 2143(I)(B) states that “simple substitution of one known element for another to obtain predictable results” may be obvious.
Modified Wei does not explicitly teach covalent bonds between the semiconductor composition and the metal being configured for CO2 activation and being present at an interface between each nanoparticle of the plurality of nanoparticles and a respective conductive projection of the array of conductive projections. Wei does however teach the nanoparticles receiving light-generated electrons reach from the nanowire conductive projections to facilitate the photoelectrochemical reaction (see e.g. Wei Page 12533, Col. 1, lines 6-12).
Zhang teaches a structure comprising semiconductor nanowires decorated with ultrasmall metal oxide cocatalyst clusters for a photocatalytic reaction (see e.g. Abstract and Page 1, Col. 2, paragraph starting with “The performance”, lines 3-10), wherein direct, covalent bonds are formed between the clusters and nanowires, thereby inducing efficient transfer of photo-generated electron from the nanowires to the clusters (see e.g. Page 4, Col. 1, lines 6-11, Page 5, Col. 2, lines 28-30 and Page 6, Col. 1, lines 7-10).
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 electrode of modified Wei to comprise direct, covalent bonds formed at the interfaces between the nanoparticles and the nanowire conductive projections as taught by Zhang to induce efficient transfer of the light-generated electrons from the nanowire conductive projections to the nanoparticles.
Modified Wei does not teach the covalent bonds being nitride bonds, as the semiconductor composition is only taught to comprise silicon (see e.g. Wei Fig. 1a, Si NWs).
Vanka teaches a photocathode (see e.g. Abstract) comprising GaN nanowires formed on an Si substrate (see e.g. Fig. 2a and Page 6531, Col. 1, lines 7-13), the GaN nanowires protecting the Si surface from corrosion and reducing charge carrier transfer resistance at the semiconductor/liquid junction, leading to long-term stability at a large current density under sun illumination (see e.g. Abstract). Covalent bonds between such GaN nanowires and attached nanoparticles would necessarily be limited to either with gallium or nitrogen, i.e. nitride bonds.
Cui similarly teaches GaN nanowires coated with Pt nanoparticles (see e.g. Abstract), wherein the Pt forms Pt—N and Pt—Ga covalent bonds with the GaN nanowires (see e.g. Fig. 8 and Page 22445, Col. 1, lines 1-6).
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 conductive projections of modified Wei to comprise GaN instead of Si as taught by Vanka to protect the Si substrate surface from corrosion and reduce charge carrier transfer resistance at the semiconductor/liquid junction, leading to long-term stability at a large current density under sun illumination, and to thereby form a covalent nitride bond to the nanoparticles as taught by Cui one of two options for forming a covalent bond between GaN and attached nanoparticles. MPEP § 2143(I)(E) states that it may be obvious to choose “from a finite number of identified, predictable solutions, with a reasonable expectation of success”.
The limitation of the covalent nitride bonds being “for CO2 activation” 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.”. Paragraph 0078 of the instant specification describes that the covalent bond indicates strong electronic coupling/interaction between the nanoparticles and nanowires, which is likely useful for CO2 activation. Modified Wei teaches all the structural elements of the claimed electrode, including the covalent nitride bonds, as stated above, and would therefore likely be similarly useful for CO2 activation.
Regarding claim 2, modified Wei teaches the substrate comprising a semiconductor material; and the semiconductor material being configured to generate charge carriers upon absorption of solar radiation such that the chemical cell is configured as a photoelectrochemical system (see e.g. Wei Page 12533, Col. 1, lines 10-12, Si, including the base, absorbing light and generating electrons, i.e. charge carriers).
Regarding claim 3, modified Wei teaches each conductive projection of the array of conductive projections comprising a nanowire configured to extract the charge carriers generated in the substrate (see e.g. Wei Page 12531, Col. 2, lines 3-6, and Page 12533, Col. 1, lines 6-12, increased reaction current density with Si NWs indicative extraction of generated electrons from charge separation).
Regarding claim 4, modified Wei teaches the substrate comprising silicon (see e.g. Wei Fig. 1a, Si wafer base).
Regarding claim 5, Wei as modified by Vanka teaches the semiconductor composition comprising gallium nitride (see e.g. Vanka Fig. 2a and Page 6531, Col. 1, lines 7-13).
Regarding claim 6, Wei as modified by Luc teaches the metallic composition comprising tin (see e.g. Luc Scheme 1, Sn in core and shell).
Regarding claim 7, Wei as modified by Luc teaches the metal oxide comprising a tin oxide (see e.g. Luc Scheme 1, SnOx shell).
Regarding claim 8, Wei as modified by Zhang teaches covalent bonds being present at an interface between each nanoparticle of the plurality of nanoparticles and a respective conductive projection of the array of conductive projections (see e.g. Zhang Page 4, Col. 1, lines 6-11, Page 5, Col. 2, lines 28-30 and Page 6, Col. 1, lines 7-10, direct, covalent bonds formed between the clusters and nanowires).
Regarding claim 10, Wei as modified by Vanka teaches the lateral dimension of each conductive projection being 40 nm (see e.g. Vanka Fig. 2a and Page 6531, Col. 1, lines 7-13 and 27-32, 40 nm GaN nanowires)
Regarding claim 11, the chemical cell being a thermochemical cell 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 Wei teaches all the structural limitations of the electrode of claim 1 as stated above, which would therefore be capable of use in a thermochemical cell.
Regarding claim 12, Wei as modified by Luc teaches an electrochemical system comprising a working electrode configured in accordance with the electrode of claim 1 (see e.g. Wei Fig. S1 and Page 12531, Col. 1, bottom paragraph, lines 1-3, cell for photoelectrocatalytic reduction comprising the metal/SiNWs electrode as the working photocathode), and further comprising:
a counter electrode (see e.g. Wei Page 12531, Col. 1, bottom paragraph, line 4, platinum plate counter electrode);
an electrolyte in which the working and counter electrodes are immersed (see e.g. Page 12531, Col. 1, bottom paragraph, lines 3-6, working photocathode and counter electrode in aqueous electrolyte); and
a voltage source that applies a bias voltage between the working and counter electrodes (see e.g. Wei Fig. S1 and Page 12535, Col. 1, under “Photoelectrochemical and electrochemical measurements”, lines 2 and 8, electrochemical station applying potential between working and counter electrodes);
wherein the bias voltage is set to a level for conversion of CO2 into formic acid at the working electrode (see e.g. Wei Table S1, HCOOH produced at -1.0 V on Ag/SiNWs photocathode; see e.g. Luc Page 1891, Col. 1, lines 5-9, HCOOH formation).
Claim 9 is rejected under 35 U.S.C. 103 as being unpatentable over Wei, Luc, Zhang, Vanka and Cui, as applied to claim 1 above, and further in view of Norton et al. (U.S. 2010/0243020).
Regarding claim 9, modified Wei teaches all the elements of the electrode of claim 1 as stated above. Modified Wei does not explicitly teach the size of each nanoparticle of the plurality of nanoparticles falling in a range from about 2 nanometers to about 3 nanometers, but does teach the size being 4.2 nanometers (see e.g. Wei Fig. 2 and Table 1, Ag-4.2/SiNWs), which is close to the claimed range. Wei does however teach the electrode being used for solar energy-assisted electroreduction (see e.g. Wei Page 12530, Col. 1, lines 8-12, and Page 12531, Col. 1, lines 6-8).
MPEP § 2144.05 I states that “a prima facie case of obviousness exists where the claimed ranges or amounts do not overlap with the prior art but are merely close.”
Furthermore, Norton teaches a solar energy capture and conversion device (see e.g. Abstract and Paragraph 0007, lines 1-2), comprising semiconductor nanostructures such as nanowires with diameters of 1 to 1000 nm (see e.g. Paragraph 0038, lines 21-29) decorated with metal nanoparticles with sizes of 100 nm or less, particularly 5 nm or less (see e.g. Abstract and Paragraph 0081, lines 1-10), encompassing the claimed range of the present invention, the sizes of which may be selected to tune an absorption spectrum of the device (see e.g. Paragraph 0081, lines 10-14).
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 nanoparticles of modified Wei to generally have a size of less than 5 nm as taught by Norton as a nanoparticle size suitable to be applied to nanowire projections used in solar capture and conversion. 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.”
Response to Arguments
Applicant’s arguments, see pages 4-5, filed 01/02/2026, with respect to the rejection(s) of amended claim(s) 1 under 35 USC 103 over Wei in view of Luc, particularly regarding the covalent nitride bonds, 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 Wei, Luc, Zhang, Vanka and Cui.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). 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.
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/M.S.J./Examiner, Art Unit 1795
/LUAN V VAN/Supervisory Patent Examiner, Art Unit 1795