Ultrafast recombination dynamics in dye-sensitized SnO2/TiO2 core/shell films

Gish, Melissa K.; Lapides, Alexander M.; Brennaman, M. Kyle; Templeton, Joseph L.; Meyer, Thomas J.; Papanikolas, John M.

doi:10.1021/acs.jpclett.6b02388

Ultrafast recombination dynamics in dye-sensitized SnO₂/TiO₂ core/shell films

Journal Article · Fri Dec 02 00:00:00 EST 2016 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.6b02388· OSTI ID:1335127

Gish, Melissa K. ^[1]; Lapides, Alexander M. ^[2]; Brennaman, M. Kyle ^[2]; Templeton, Joseph L. ^[2]; Meyer, Thomas J. ^[2]; ^[2]

Univ. of North Carolina, Chapel Hill, NC (United States); UNC Chapel Hill
Univ. of North Carolina, Chapel Hill, NC (United States)

In dye-sensitized photoelectrosynthesis cells (DSPECs), molecular chromophores and catalysts are integrated on a semiconductor surface to perform water oxidation or CO₂ reduction after a series of light-induced electron transfer events. Unfortunately, recombination of the charge separated state (CSS) is competitive with productive catalysis. To overcome this major obstacle, implementation of photoanodic core/shell films within these devices improve electrochemical behavior and slow recombination through the introduction of an energetic barrier between the semiconductor core and oxidized species on the surface. In this study, interfacial dynamics are investigated in SnO₂/TiO₂ core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([RuII(bpy)2(4,4'-(PO₃H₂)₂bpy)]²⁺, RuP) using transient absorption methods. Electron injection from the chromophore into the TiO₂ shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived CSS depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO₂ core and must tunnel through the TiO₂ shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of DSPECs.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC); Univ. of North Carolina, Chapel Hill, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001011

OSTI ID:: 1335127

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Vol. 7; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (30)

Molecular Chromophore–Catalyst Assemblies for Solar Fuel Applications Ashford, Dennis L.; Gish, Melissa K.; Vannucci, Aaron K. Chemical Reviews, Vol. 115, Issue 23 https://doi.org/10.1021/acs.chemrev.5b00229	journal	August 2015
Charge Recombination Dynamics in Sensitized SnO ₂ /TiO ₂ Core/Shell Photoanodes Knauf, Robin R.; Kalanyan, Berç; Parsons, Gregory N. The Journal of Physical Chemistry C, Vol. 119, Issue 51 https://doi.org/10.1021/acs.jpcc.5b10574	journal	December 2015
Ultrafast Electron Injection Dynamics of Photoanodes for Water-Splitting Dye-Sensitized Photoelectrochemical Cells Swierk, John R.; McCool, Nicholas S.; Nemes, Coleen T. The Journal of Physical Chemistry C, Vol. 120, Issue 11 https://doi.org/10.1021/acs.jpcc.6b00749	journal	March 2016
Light-Driven Water Splitting with a Molecular Electroassembly-Based Core/Shell Photoanode Sherman, Benjamin D.; Ashford, Dennis L.; Lapides, Alexander M. The Journal of Physical Chemistry Letters, Vol. 6, Issue 16 https://doi.org/10.1021/acs.jpclett.5b01370	journal	July 2015
Dynamics of Electron Injection in SnO ₂ /TiO ₂ Core/Shell Electrodes for Water-Splitting Dye-Sensitized Photoelectrochemical Cells McCool, Nicholas S.; Swierk, John R.; Nemes, Coleen T. The Journal of Physical Chemistry Letters, Vol. 7, Issue 15 https://doi.org/10.1021/acs.jpclett.6b01528	journal	July 2016
Probing the Optical Property and Electronic Structure of TiO ₂ Nanomaterials for Renewable Energy Applications Kapilashrami, Mukes; Zhang, Yanfeng; Liu, Yi-Sheng Chemical Reviews, Vol. 114, Issue 19 https://doi.org/10.1021/cr5000893	journal	May 2014
Tunable Energy Transfer Rates via Control of Primary, Secondary, and Tertiary Structure of a Coiled Coil Peptide Scaffold Wilger, Dale J.; Bettis, Stephanie E.; Materese, Christopher K. Inorganic Chemistry, Vol. 51, Issue 21 https://doi.org/10.1021/ic300669t	journal	June 2012
Sensitization of TiO ₂ by Phosphonate-Derivatized Proline Assemblies Trammell, Scott A.; Moss, John A.; Yang, John C. Inorganic Chemistry, Vol. 38, Issue 16 https://doi.org/10.1021/ic990052t	journal	July 1999
Control of Charge Recombination Dynamics in Dye Sensitized Solar Cells by the Use of Conformally Deposited Metal Oxide Blocking Layers Palomares, Emilio; Clifford, John N.; Haque, Saif A. Journal of the American Chemical Society, Vol. 125, Issue 2 https://doi.org/10.1021/ja027945w	journal	January 2003
Photoinduced Electron Injection from Ru(dcbpy) ₂ (NCS) ₂ to SnO ₂ and TiO ₂ Nanocrystalline Films Benkö, Gábor; Myllyperkiö, Pasi; Pan, Jie Journal of the American Chemical Society, Vol. 125, Issue 5 https://doi.org/10.1021/ja029025j	journal	February 2003
Biohybrid Photosynthetic Antenna Complexes for Enhanced Light-Harvesting Springer, Joseph W.; Parkes-Loach, Pamela S.; Reddy, Kanumuri Ramesh Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja207390y	journal	February 2012
Interfacial Energy Conversion in Ru ^II Polypyridyl-Derivatized Oligoproline Assemblies on TiO ₂ Ma, Da; Bettis, Stephanie E.; Hanson, Kenneth Journal of the American Chemical Society, Vol. 135, Issue 14 https://doi.org/10.1021/ja312143h	journal	March 2013
Systematic Modulation of Quantum (Electron) Tunneling Behavior by Atomic Layer Deposition on Nanoparticulate SnO ₂ and TiO ₂ Photoanodes Prasittichai, Chaiya; Avila, Jason R.; Farha, Omar K. Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja4089555	journal	October 2013
Disentangling the Physical Processes Responsible for the Kinetic Complexity in Interfacial Electron Transfer of Excited Ru(II) Polypyridyl Dyes on TiO ₂ Zigler, David F.; Morseth, Zachary A.; Wang, Li Journal of the American Chemical Society, Vol. 138, Issue 13 https://doi.org/10.1021/jacs.5b12996	journal	March 2016
Electron Injection Dynamics of Ru Polypyridyl Complexes on SnO ₂ Nanocrystalline Thin Films Ai, Xin; Anderson, Neil A.; Guo, Jianchang The Journal of Physical Chemistry B, Vol. 109, Issue 15 https://doi.org/10.1021/jp046037d	journal	April 2005
Comparison of Interfacial Electron Transfer through Carboxylate and Phosphonate Anchoring Groups ^† She, Chunxing; Guo, Jianchang; Irle, Stephan The Journal of Physical Chemistry A, Vol. 111, Issue 29 https://doi.org/10.1021/jp0709003	journal	July 2007
Structure–Property Relationships in Phosphonate-Derivatized, Ru ^II Polypyridyl Dyes on Metal Oxide Surfaces in an Aqueous Environment Hanson, Kenneth; Brennaman, M. Kyle; Ito, Akitaka The Journal of Physical Chemistry C, Vol. 116, Issue 28 https://doi.org/10.1021/jp304088d	journal	July 2012
Revealing the Relationship between Semiconductor Electronic Structure and Electron Transfer Dynamics at Metal Oxide–Chromophore Interfaces Knauf, Robin R.; Brennaman, M. Kyle; Alibabaei, Leila The Journal of Physical Chemistry C, Vol. 117, Issue 48 https://doi.org/10.1021/jp407587r	journal	November 2013
Watching Photoactivation in a Ru(II) Chromophore–Catalyst Assembly on TiO ₂ by Ultrafast Spectroscopy Wang, Li; Ashford, Dennis L.; Thompson, David W. The Journal of Physical Chemistry C, Vol. 117, Issue 46 https://doi.org/10.1021/jp410571x	journal	November 2013
Photophysical Characterization of a Helical Peptide Chromophore–Water Oxidation Catalyst Assembly on a Semiconductor Surface Using Ultrafast Spectroscopy Bettis, Stephanie E.; Ryan, Derek M.; Gish, Melissa K. The Journal of Physical Chemistry C, Vol. 118, Issue 12 https://doi.org/10.1021/jp410646u	journal	March 2014
Photophysical Characterization of a Chromophore/Water Oxidation Catalyst Containing a Layer-by-Layer Assembly on Nanocrystalline TiO ₂ Using Ultrafast Spectroscopy Bettis, Stephanie E.; Hanson, Kenneth; Wang, Li The Journal of Physical Chemistry A, Vol. 118, Issue 45 https://doi.org/10.1021/jp411139j	journal	May 2014
Electron Mobility and Injection Dynamics in Mesoporous ZnO, SnO ₂ , and TiO ₂ Films Used in Dye-Sensitized Solar Cells Tiwana, Priti; Docampo, Pablo; Johnston, Michael B. ACS Nano, Vol. 5, Issue 6 https://doi.org/10.1021/nn201243y	journal	May 2011
Photodriven heterogeneous charge transfer with transition-metal compounds anchored to TiO ₂ semiconductor surfaces Ardo, Shane; Meyer, Gerald J. Chem. Soc. Rev., Vol. 38, Issue 1 https://doi.org/10.1039/B804321N	journal	January 2009
Slow charge recombination in dye-sensitised solar cells (DSSC) using Al2O3 coated nanoporous TiO2 films Palomares, Emilio; Clifford, John N.; Haque, Saif A. Chemical Communications, Issue 14 https://doi.org/10.1039/b202515a	journal	June 2002
Chemical approaches to artificial photosynthesis Concepcion, J. J.; House, R. L.; Papanikolas, J. M. Proceedings of the National Academy of Sciences, Vol. 109, Issue 39 https://doi.org/10.1073/pnas.1212254109	journal	September 2012
Solar water splitting in a molecular photoelectrochemical cell Alibabaei, L.; Brennaman, M. K.; Norris, M. R. Proceedings of the National Academy of Sciences, Vol. 110, Issue 50 https://doi.org/10.1073/pnas.1319628110	journal	November 2013
Visible photoelectrochemical water splitting into H ₂ and O ₂ in a dye-sensitized photoelectrosynthesis cell Alibabaei, Leila; Sherman, Benjamin D.; Norris, Michael R. Proceedings of the National Academy of Sciences, Vol. 112, Issue 19 https://doi.org/10.1073/pnas.1506111112	journal	April 2015
Amorphous TiO2 coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation Hu, S.; Shaner, M. R.; Beardslee, J. A. Science, Vol. 344, Issue 6187 https://doi.org/10.1126/science.1251428	journal	May 2014
Ultrafast studies of electron injection in Ru dye sensitized SnO 2 nanocrystalline thin film Bauer, Christophe; Boschloo, Gerrit; Mukhtar, Emad International Journal of Photoenergy, Vol. 4, Issue 1 https://doi.org/10.1155/S1110662X0200003X	journal	January 2002
Dye-sensitized Solar Cells Employing a SnO₂-TiO₂ Core-shell Structure Made by Atomic Layer Deposition Karlsson, Martin; Jõgi, Indrek; Eriksson, Susanna K. CHIMIA International Journal for Chemistry, Vol. 67, Issue 3 https://doi.org/10.2533/chimia.2013.142	journal	March 2013

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Bio-inspired model of photosystem II: supramolecular assembly of an electron mediator into an SnO ₂ photoanode co-sensitized by a porphyrin photosensitizer and ruthenium molecular catalyst Na, Yong; Miao, Siwen; Zhou, Li Sustainable Energy & Fuels, Vol. 2, Issue 3 https://doi.org/10.1039/c7se00515f	journal	January 2018
Long-lived charge separation in dye–semiconductor assemblies: a pathway to multi-electron transfer reactions Sundin, Elin; Abrahamsson, Maria Chemical Communications, Vol. 54, Issue 42 https://doi.org/10.1039/c8cc01071d	journal	January 2018
Core–shell structured titanium dioxide nanomaterials for solar energy utilization Li, Wei; Elzatahry, Ahmed; Aldhayan, Dhaifallah Chemical Society Reviews, Vol. 47, Issue 22 https://doi.org/10.1039/c8cs00443a	journal	January 2018
Barriers for interfacial back-electron transfer: A comparison between TiO ₂ and SnO ₂ /TiO ₂ core/shell structures Troian-Gautier, Ludovic; Sampaio, Renato N.; Piechota, Eric J. The Journal of Chemical Physics, Vol. 150, Issue 4 https://doi.org/10.1063/1.5054604	journal	January 2019

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