Heterobinuclear Light Absorber Coupled to Molecular Wire for Charge Transport across Ultrathin Silica Membrane for Artificial Photosynthesis

Katsoukis, Georgios; Frei, Heinz

doi:10.1021/acsami.8b11684

Title: Heterobinuclear Light Absorber Coupled to Molecular Wire for Charge Transport across Ultrathin Silica Membrane for Artificial Photosynthesis

Journal Article · Mon Aug 27 00:00:00 EDT 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.8b11684· OSTI ID:1786329

Katsoukis, Georgios ^[1];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

Coupling of robust, all-inorganic heterobinuclear light absorbers to metal oxide catalysts for water oxidation across an ultrathin product-separating silica membrane requires charge transfer through organic molecular wires embedded in the silica. A synthetic approach for assembling the bimetallic units on the silica surface is introduced that is compatible with the presence of encapsulated organic molecules. Accurate selection and fine tuning of the concentration of embedded conducting wires are enabled by a two-step method consisting of surface attachment of a tripodal anchor, trimethoxysilyl aniline, followed by attachment of p-oligo(phenylene vinylene) through amide linkage. Each step of the assembly process was monitored and characterized by a combination of Fourier transform infrared, Fourier transform-Raman, and UV-vis spectroscopy techniques. Hole transfer was observed from transient Co^III, formed by Ti^IVOCo^II → Ti^IIIOCo^III charge transfer excitation of the chromophore, to p-oligo(phenylene vinylene) molecule within the 8 ns width of the photolysis laser pulse by transient optical absorption spectroscopy of the wire radical cation. The rectifying property of the light absorber-wire assembly enabled by appropriate selection of redox potentials of metals and embedded wire obviates the need for a molecularly defined linkage between the components. Combined with the previously observed ultrafast hole injection from the embedded wires to Co oxide catalyst, the result implies visible-light-induced hole transfer from visible-light-excited binuclear light absorber to water oxidation catalyst across the silica separation membrane in a few nanoseconds or faster. Finally, demonstration and understanding of this interfacial charge-transfer step is critical for developing nanoscale core-shell architectures for complete photosynthetic cycles.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; KA 4403/1-1

OSTI ID:: 1786329

Journal Information:: ACS Applied Materials and Interfaces, Vol. 10, Issue 37; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (39)

Optical spectra and structure of oligomeric models of polyparaphenylenevinylene Tian, B.; Zerbi, G.; Schenk, R. The Journal of Chemical Physics, Vol. 95, Issue 5 https://doi.org/10.1063/1.460875	journal	September 1991
Electronic and structural properties of polyparaphenylenevinylene from the vibrational spectra Tian, B.; Zerbi, G.; Müllen, K. The Journal of Chemical Physics, Vol. 95, Issue 5 https://doi.org/10.1063/1.460876	journal	September 1991
Directed Assembly of Cuprous Oxide Nanocatalyst for CO ₂ Reduction Coupled to Heterobinuclear ZrOCo ^II Light Absorber in Mesoporous Silica Kim, Wooyul; Frei, Heinz ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01306	journal	August 2015
Raman Spectra of Poly( p -phenylenevinylene)s with Fluorinated Vinylene Units: Evidence of Inter-ring Distortion Piacenza, Manuel; Comoretto, Davide; Burger, Martin ChemPhysChem, Vol. 10, Issue 8 https://doi.org/10.1002/cphc.200900041	journal	June 2009
Molecular Structure of 3-Aminopropyltriethoxysilane Layers Formed on Silanol-Terminated Silicon Surfaces Acres, Robert G.; Ellis, Amanda V.; Alvino, Jason The Journal of Physical Chemistry C, Vol. 116, Issue 10 https://doi.org/10.1021/jp212056s	journal	March 2012
Planarization, Fusion, and Strain of Carbon-Bridged Phenylenevinylene Oligomers Enhance π-Electron and Charge Conjugation: A Dissectional Vibrational Raman Study Burrezo, Paula Mayorga; Zhu, Xiaozhang; Zhu, Shou-Fei Journal of the American Chemical Society, Vol. 137, Issue 11 https://doi.org/10.1021/ja5125463	journal	March 2015
Fabrication of Core–Shell Nanotube Array for Artificial Photosynthesis Featuring an Ultrathin Composite Separation Membrane Edri, Eran; Aloni, Shaul; Frei, Heinz ACS Nano, Vol. 12, Issue 1 https://doi.org/10.1021/acsnano.7b07125	journal	January 2018
Photolysis of titanocene dichloride Tsai, Zei-Tsan; Brubaker, Carl H. Journal of Organometallic Chemistry, Vol. 166, Issue 2 https://doi.org/10.1016/S0022-328X(00)91634-6	journal	February 1979
Inorganic core–shell assemblies for closing the artificial photosynthetic cycle Yuan, Guangbi; Agiral, Anil; Pellet, Norman Faraday Discuss., Vol. 176 https://doi.org/10.1039/C4FD00150H	journal	January 2014
Design of All-Inorganic Molecular-Based Photocatalysts Sensitive to Visible Light: Ti(IV)−O−Ce(III) Bimetallic Assemblies on Mesoporous Silica Nakamura, Ryuhei; Okamoto, Akihiro; Osawa, Hitoshi Journal of the American Chemical Society, Vol. 129, Issue 31 https://doi.org/10.1021/ja073668n	journal	August 2007
Vibrational spectra and DFT calculations of PPV-oligomers Hrenar, T.; Mitrić, R.; Meić, Z. Journal of Molecular Structure, Vol. 661-662 https://doi.org/10.1016/S0022-2860(03)00526-X	journal	December 2003
Glass-Encapsulated Light Harvesters: More Efficient Dye-Sensitized Solar Cells by Deposition of Self-Aligned, Conformal, and Self-Limited Silica Layers Son, Ho-Jin; Wang, Xinwei; Prasittichai, Chaiya Journal of the American Chemical Society, Vol. 134, Issue 23 https://doi.org/10.1021/ja300015n	journal	May 2012
Site-Specific Synthesis of Oxo-Bridged Mixed-Valence Binuclear Complexes on Mesoporous Silica Okamoto, Akihiro; Nakamura, Ryuhei; Osawa, Hitoshi Langmuir, Vol. 24, Issue 13 https://doi.org/10.1021/la704032c	journal	July 2008
Visible Light-Induced Hole Injection into Rectifying Molecular Wires Anchored on Co ₃ O ₄ and SiO ₂ Nanoparticles Soo, Han Sen; Agiral, Anil; Bachmeier, Andreas Journal of the American Chemical Society, Vol. 134, Issue 41 https://doi.org/10.1021/ja306162g	journal	October 2012
EXAFS Spectroscopic Analysis of Heterobinuclear TiOMn Charge-Transfer Chromophore in Mesoporous Silica Soo, H. S.; Macnaughtan, M. L.; Weare, W. W. The Journal of Physical Chemistry C, Vol. 115, Issue 50 https://doi.org/10.1021/jp208419q	journal	November 2011
Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies Kim, Wooyul; McClure, Beth Anne; Edri, Eran Chemical Society Reviews, Vol. 45, Issue 11 https://doi.org/10.1039/C6CS00062B	journal	January 2016
The surface chemistry of amorphous silica. Zhuravlev model Zhuravlev, L. T. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 173, Issue 1-3 https://doi.org/10.1016/S0927-7757(00)00556-2	journal	November 2000
Heterogeneous catalysts obtained by grafting metallocene complexes onto mesoporous silica Maschmeyer, Thomas; Rey, Fernando; Sankar, Gopinathan Nature, Vol. 378, Issue 6553 https://doi.org/10.1038/378159a0	journal	November 1995
Photolysis of cyclopentadienide and cyclopentadiene Van Tamelen, Eugene E.; Brauman, John I.; Ellis, Larry E. Journal of the American Chemical Society, Vol. 93, Issue 23 https://doi.org/10.1021/ja00752a027	journal	November 1971
Photochemistry of titanocene(IV) derivatives Harrigan, R. W.; Hammond, George S.; Gray, Harry B. Journal of Organometallic Chemistry, Vol. 81, Issue 1 https://doi.org/10.1016/S0022-328X(00)87889-4	journal	November 1974
Photodriven Oxidation of Surface-Bound Iridium-Based Molecular Water-Oxidation Catalysts on Perylene-3,4-dicarboximide-Sensitized TiO ₂ Electrodes Protected by an Al ₂ O ₃ Layer Kamire, Rebecca J.; Materna, Kelly L.; Hoffeditz, William L. The Journal of Physical Chemistry C, Vol. 121, Issue 7 https://doi.org/10.1021/acs.jpcc.6b11672	journal	February 2017
The ultraviolet spectra of aniline, 2-, 3-, and 4-aminopyridines and of some of their derivatives in n-hexane, 1,4-dioxan, ethanol, and water solutions Cumper, C. W. N.; Singleton, A. Journal of the Chemical Society B: Physical Organic https://doi.org/10.1039/j29680000649	journal	January 1968
Photoinduced Electron Transfer from ZrOCo Binuclear Light Absorber to Pyridine Elucidated by Transient Optical and Infrared Spectroscopy Hill, Adam D.; Katsoukis, Georgios; Frei, Heinz The Journal of Physical Chemistry C, Vol. 122, Issue 35 https://doi.org/10.1021/acs.jpcc.8b06435	journal	August 2018
Dependence of electron transfer dynamics in wire-like bridge molecules on donor–bridge energetics and electronic interactions Davis, William B.; Ratner, Mark A.; Wasielewski, Michael R. Chemical Physics, Vol. 281, Issue 2-3 https://doi.org/10.1016/S0301-0104(02)00444-5	journal	August 2002
Nanoscale membranes that chemically isolate and electronically wire up the abiotic/biotic interface Cornejo, Jose A.; Sheng, Hua; Edri, Eran Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04707-6	journal	June 2018
Visible Light Induced Hole Transport from Sensitizer to Co ₃ O ₄ Water Oxidation Catalyst across Nanoscale Silica Barrier with Embedded Molecular Wires Agiral, Anil; Soo, Han Sen; Frei, Heinz Chemistry of Materials, Vol. 25, Issue 11 https://doi.org/10.1021/cm400759f	journal	May 2013
Visible light absorption of binuclear TiOCoII charge-transfer unit assembled in mesoporous silica Han, Hongxian; Frei, Heinz Microporous and Mesoporous Materials, Vol. 103, Issue 1-3 https://doi.org/10.1016/j.micromeso.2007.02.010	journal	June 2007
Photodriven hydrogen evolution by molecular catalysts using Al ₂ O ₃ -protected perylene-3,4-dicarboximide on NiO electrodes Kamire, Rebecca J.; Majewski, Marek B.; Hoffeditz, William L. Chemical Science, Vol. 8, Issue 1 https://doi.org/10.1039/C6SC02477G	journal	January 2017
Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation Vannucci, A. K.; Alibabaei, L.; Losego, M. D. Proceedings of the National Academy of Sciences, Vol. 110, Issue 52 https://doi.org/10.1073/pnas.1319832110	journal	November 2013
Charge Transport through Organic Molecular Wires Embedded in Ultrathin Insulating Inorganic Layer Edri, Eran; Frei, Heinz The Journal of Physical Chemistry C, Vol. 119, Issue 51 https://doi.org/10.1021/acs.jpcc.5b09994	journal	December 2015
Synthesis, characterization, and water oxidation by a molecular chromophore-catalyst assembly prepared by atomic layer deposition. The “mummy” strategy Lapides, A. M.; Sherman, B. D.; Brennaman, M. K. Chemical Science, Vol. 6, Issue 11 https://doi.org/10.1039/C5SC01752A	journal	January 2015
Ultrafast Charge Transfer between Light Absorber and Co ₃ O ₄ Water Oxidation Catalyst across Molecular Wires Embedded in Silica Membrane Edri, Eran; Cooper, Jason K.; Sharp, Ian D. Journal of the American Chemical Society, Vol. 139, Issue 15 https://doi.org/10.1021/jacs.7b01070	journal	April 2017
A Novel Approach to the Synthesis of 1,3,3-trinitroazetidine Marchand, Alan P.; Rajagopal, D.; Bott, Simon G. The Journal of Organic Chemistry, Vol. 60, Issue 15 https://doi.org/10.1021/jo00120a049	journal	July 1995
Single-Step Dispersion of Functionalities on a Silica Surface Banet, Philippe; Marcotte, Nathalie; Lerner, Dan A. Langmuir, Vol. 24, Issue 16 https://doi.org/10.1021/la800745g	journal	July 2008
Light Induced Carbon Dioxide Reduction by Water at Binuclear ZrOCo ^II Unit Coupled to Ir Oxide Nanocluster Catalyst Kim, Wooyul; Yuan, Guangbi; McClure, Beth Anne Journal of the American Chemical Society, Vol. 136, Issue 31 https://doi.org/10.1021/ja504753g	journal	July 2014
Anion and cation absorption spectra of conjugated oligomers and polymers Deussen, M.; Bässler, H. Chemical Physics, Vol. 164, Issue 2 https://doi.org/10.1016/0301-0104(92)87148-3	journal	August 1992
Binuclear ZrOCo Metal-to-Metal Charge-Transfer Unit in Mesoporous Silica for Light-Driven CO ₂ Reduction to CO and Formate Macnaughtan, Marisa L.; Soo, Han Sen; Frei, Heinz The Journal of Physical Chemistry C, Vol. 118, Issue 15 https://doi.org/10.1021/jp5014994	journal	April 2014
In Situ Spectroscopy of Water Oxidation at Ir Oxide Nanocluster Driven by Visible TiOCr Charge-transfer Chromophore in Mesoporous Silica Han, Hongxian; Frei, Heinz The Journal of Physical Chemistry C, Vol. 112, Issue 41 https://doi.org/10.1021/jp803994d	journal	September 2008
Hierarchical Inorganic Assemblies for Artificial Photosynthesis Kim, Wooyul; Edri, Eran; Frei, Heinz Accounts of Chemical Research, Vol. 49, Issue 9 https://doi.org/10.1021/acs.accounts.6b00182	journal	August 2016

Cited By (2)

Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid‐to‐Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen Jo, Won Jun; Katsoukis, Georgios; Frei, Heinz Advanced Functional Materials, Vol. 30, Issue 12 https://doi.org/10.1002/adfm.201909262	journal	February 2020
Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems Katsoukis, Georgios; Frei, Heinz The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5052453	journal	January 2019

Similar Records

Photoinduced Electron Transfer from ZrOCo Binuclear Light Absorber to Pyridine Elucidated by Transient Optical and Infrared Spectroscopy

Journal Article · Thu Aug 09 00:00:00 EDT 2018 · Journal of Physical Chemistry. C · OSTI ID:1786329

Hill, Adam D.; Katsoukis, Georgios; Frei, Heinz

Ultrafast Charge Transfer between Light Absorber and Co₃O₄ Water Oxidation Catalyst across Molecular Wires Embedded in Silica Membrane

Journal Article · Wed Mar 29 00:00:00 EDT 2017 · Journal of the American Chemical Society · OSTI ID:1786329

Edri, Eran; Cooper, Jason K.; Sharp, Ian D.; +2 more

Hierarchical Inorganic Assemblies for Artificial Photosynthesis

Journal Article · Tue Aug 30 00:00:00 EDT 2016 · Accounts of Chemical Research · OSTI ID:1786329

Kim, Wooyul; Edri, Eran; Frei, Heinz

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
artificial photosynthesis
silica membrane
charge transfer
molecular wire
surface anchoring
transient optical spectroscopy

Title: Heterobinuclear Light Absorber Coupled to Molecular Wire for Charge Transport across Ultrathin Silica Membrane for Artificial Photosynthesis

Citation Formats

References (39)

Cited By (2)

Similar Records

Related Subjects