Charge Recombination with Fractional Reaction Orders in Water-Splitting Dye-sensitized Photoelectrochemical Cells

Xu, Pengtao; Gray, Christopher L.; Xiao, Langqiu; Mallouk, Thomas E.

doi:10.1021/jacs.8b04878

Title: Charge Recombination with Fractional Reaction Orders in Water-Splitting Dye-sensitized Photoelectrochemical Cells

Journal Article · Mon Aug 27 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b04878· OSTI ID:1466648

Xu, Pengtao ^[1]; Gray, Christopher L. ^[1]; Xiao, Langqiu ^[1]; Mallouk, Thomas E. ^[1]

The Pennsylvania State Univ., University Park, PA (United States)

In water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs), charge recombination competes with catalytic water oxidation to determine the overall efficiency of the system. The kinetics of these processes have been difficult to understand because transient absorbance (TA) experiments typically show nearly complete charge recombination on the sub-millisecond timescale; in contrast, electrochemical measurements such as open circuit photovoltage decay suggest a charge recombination timescale that is 2-3 orders of magnitude longer. Here we explore these processes with dye-sensitized nanocrystalline TiO₂ and TiO₂/Ta₂O₅ core-shell photoanodes in aqueous electrolytes using TA spectroscopy, intensity-modulated photovoltage spectroscopy (IMVS), and photoelectrochemical impedance spectroscopy (PEIS). The fast recombination rates measured by TA result from strong laser excitation that leads to high electron occupancy in TiO₂, whereas IMVS modulates the concentration of charge-separated states near solar irradiance levels. The recombination processes measured by electrochemical methods such as IMVS, PEIS, and transient photovoltage are the discharging of injected electrons in TiO₂, as evidenced by the close agreement betweeen the nearly first-order recombination rates probed by IMVS and the RC time constants derived from PEIS data. However, IMVS measurements at variable probe light intensity reveal that the reaction orders for the recombination of injected electrons with oxidized sensitizer molecules are far from unity. In conclusion, this kinetic analysis is relevant to understanding steady-state recombination rates in full WS-DSPECs in which molecular and nanoparticle catalysts are used to oxidize water.

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Research Organization:: Pennsylvania State Univ., University Park, PA (United States)

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

Grant/Contract Number:: FG02-07ER15911

OSTI ID:: 1466648

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 37; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 30 works

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References (39)

Finding the Way to Solar Fuels with Dye-Sensitized Photoelectrosynthesis Cells Brennaman, M. Kyle; Dillon, Robert J.; Alibabaei, Leila Journal of the American Chemical Society, Vol. 138, Issue 40 https://doi.org/10.1021/jacs.6b06466	journal	September 2016
Water splitting dye-sensitized solar cells Xu, Pengtao; McCool, Nicholas S.; Mallouk, Thomas E. Nano Today, Vol. 14 https://doi.org/10.1016/j.nantod.2017.04.009	journal	June 2017
Device Fabrication for Water Oxidation, Hydrogen Generation, and CO2 Reduction via Molecular Engineering Li, Fusheng; Yang, Hao; Li, Wenlong Joule, Vol. 2, Issue 1 https://doi.org/10.1016/j.joule.2017.10.012	journal	January 2018
Photoassisted Overall Water Splitting in a Visible Light-Absorbing Dye-Sensitized Photoelectrochemical Cell Youngblood, W. Justin; Lee, Seung-Hyun Anna; Kobayashi, Yoji Journal of the American Chemical Society, Vol. 131, Issue 3, p. 926-927 https://doi.org/10.1021/ja809108y	journal	January 2009
Direct observation of sequential oxidations of a titania-bound molecular proxy catalyst generated through illumination of molecular sensitizers Chen, Hsiang-Yun; Ardo, Shane Nature Chemistry, Vol. 10, Issue 1 https://doi.org/10.1038/nchem.2892	journal	November 2017
Direct Interfacial Electron Transfer from High-Potential Porphyrins into Semiconductor Surfaces: A Comparison of Linkers and Anchoring Groups Jiang, Jianbing; Spies, Jacob A.; Swierk, John R. The Journal of Physical Chemistry C, Vol. 122, Issue 25 https://doi.org/10.1021/acs.jpcc.7b12405	journal	December 2017
Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer Brennan, Bradley J.; Regan, Kevin P.; Durrell, Alec C. ACS Energy Letters, Vol. 2, Issue 1 https://doi.org/10.1021/acsenergylett.6b00583	journal	December 2016
Sensitization of Nanocrystalline TiO ₂ Initiated by Reductive Quenching of Molecular Excited States Thompson, David W.; Kelly, Craig A.; Farzad, Fereshteh Langmuir, Vol. 15, Issue 3 https://doi.org/10.1021/la980809d	journal	February 1999
Effects of Bridging Ligands on the Current−Potential Behavior and Interfacial Kinetics of Ruthenium-Sensitized Nanocrystalline TiO ₂ Photoelectrodes ^† Kilså, Kristine; Mayo, Elizabeth I.; Kuciauskas, Darius The Journal of Physical Chemistry A, Vol. 107, Issue 18 https://doi.org/10.1021/jp021921u	journal	May 2003
Cation-Controlled Interfacial Charge Injection in Sensitized Nanocrystalline TiO ₂ Kelly, Craig A.; Farzad, Fereshteh; Thompson, David W. Langmuir, Vol. 15, Issue 20 https://doi.org/10.1021/la990617y	journal	September 1999
Parameters Influencing Charge Recombination Kinetics in Dye-Sensitized Nanocrystalline Titanium Dioxide Films Haque, Saif A.; Tachibana, Yasuhiro; Willis, Richard L. The Journal of Physical Chemistry B, Vol. 104, Issue 3 https://doi.org/10.1021/jp991085x	journal	January 2000
Ostwald Isolation to Determine the Reaction Order for TiO ₂ (e ^– )\|S ⁺ → TiO ₂ \|S Charge Recombination at Sensitized TiO ₂ Interfaces Brigham, Erinn C.; Meyer, Gerald J. The Journal of Physical Chemistry C, Vol. 118, Issue 15 https://doi.org/10.1021/jp501814r	journal	April 2014
A generalized theory of intensity modulated photocurrent spectroscopy (IMPS) Ponomarev, E. A.; Peter, L. M. Journal of Electroanalytical Chemistry, Vol. 396, Issue 1-2 https://doi.org/10.1016/0022-0728(95)04115-5	journal	October 1995
Band Edge Movement and Recombination Kinetics in Dye-Sensitized Nanocrystalline TiO ₂ Solar Cells: A Study by Intensity Modulated Photovoltage Spectroscopy Schlichthörl, G.; Huang, S. Y.; Sprague, J. The Journal of Physical Chemistry B, Vol. 101, Issue 41 https://doi.org/10.1021/jp9714126	journal	October 1997
Charge Transport and Back Reaction in Solid-State Dye-Sensitized Solar Cells: A Study Using Intensity-Modulated Photovoltage and Photocurrent Spectroscopy Krüger, Jessica; Plass, Robert; Grätzel, Michael The Journal of Physical Chemistry B, Vol. 107, Issue 31 https://doi.org/10.1021/jp0348777	journal	August 2003
Characterization of Planar Lead Halide Perovskite Solar Cells by Impedance Spectroscopy, Open-Circuit Photovoltage Decay, and Intensity-Modulated Photovoltage/Photocurrent Spectroscopy Pockett, Adam; Eperon, Giles E.; Peltola, Timo The Journal of Physical Chemistry C, Vol. 119, Issue 7 https://doi.org/10.1021/jp510837q	journal	February 2015
Understanding the origin of photoelectrode performance enhancement by probing surface kinetics Thorne, James E.; Jang, Ji-Wook; Liu, Erik Y. Chemical Science, Vol. 7, Issue 5 https://doi.org/10.1039/C5SC04519C	journal	January 2016
Dye-Sensitized Solar Cells Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr900356p	journal	November 2010
Influence of the TiCl ₄ Treatment on Nanocrystalline TiO ₂ Films in Dye-Sensitized Solar Cells. 2. Charge Density, Band Edge Shifts, and Quantification of Recombination Losses at Short Circuit O'Regan, Brian C.; Durrant, James R.; Sommeling, Paul M. The Journal of Physical Chemistry C, Vol. 111, Issue 37 https://doi.org/10.1021/jp073056p	journal	August 2007
Adjustment of Conduction Band Edge of Compact TiO ₂ Layer in Perovskite Solar Cells Through TiCl ₄ Treatment Murakami, Takurou N.; Miyadera, Tetsuhiko; Funaki, Takashi ACS Applied Materials & Interfaces, Vol. 9, Issue 42 https://doi.org/10.1021/acsami.7b07496	journal	October 2017
Influence of the concentration of TiCl4 solution used for post-treatment on mesoporous TiO2 layers in hybrid lead halide perovskite solar cells Choe, Geunpyo; Kang, Jinhyun; Ryu, Ilhwan Solar Energy, Vol. 155 https://doi.org/10.1016/j.solener.2017.07.065	journal	October 2017
Effects of TiCl ₄ treatment on the structural and electrochemical properties of a porous TiO ₂ layer in CH ₃ NH ₃ PbI ₃ perovskite solar cells Adli, Hasyiya Karimah; Harada, Takashi; Nakanishi, Shuji Phys. Chem. Chem. Phys., Vol. 19, Issue 39 https://doi.org/10.1039/C7CP04132B	journal	January 2017
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
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
Ultrafast Recombination Dynamics in Dye-Sensitized SnO ₂ /TiO ₂ Core/Shell Films Gish, Melissa K.; Lapides, Alexander M.; Brennaman, M. Kyle The Journal of Physical Chemistry Letters, Vol. 7, Issue 24 https://doi.org/10.1021/acs.jpclett.6b02388	journal	November 2016
Charge Recombination in Dye-Sensitized Nanocrystalline TiO ₂ Solar Cells Huang, S. Y.; Schlichthörl, G.; Nozik, A. J. The Journal of Physical Chemistry B, Vol. 101, Issue 14 https://doi.org/10.1021/jp962377q	journal	April 1997
The effect of temperature on the charge transport and transient absorption properties of K27 sensitized DSSC Ocakoglu, Kasim; Yakuphanoglu, Fahrettin; Durrant, James R. Solar Energy Materials and Solar Cells, Vol. 92, Issue 9 https://doi.org/10.1016/j.solmat.2008.03.006	journal	September 2008
Simulation and measurement of complete dye sensitised solar cells: including the influence of trapping, electrolyte, oxidised dyes and light intensity on steady state and transient device behaviour Barnes, Piers R. F.; Anderson, Assaf Y.; Durrant, James R. Physical Chemistry Chemical Physics, Vol. 13, Issue 13 https://doi.org/10.1039/c0cp01554g	journal	January 2011
Proton-Induced Trap States, Injection and Recombination Dynamics in Water-Splitting Dye-Sensitized Photoelectrochemical Cells McCool, Nicholas S.; Swierk, John R.; Nemes, Coleen T. ACS Applied Materials & Interfaces, Vol. 8, Issue 26 https://doi.org/10.1021/acsami.6b05362	journal	June 2016
Phosphonate-Based Bipyridine Dyes for Stable Photovoltaic Devices Gillaizeau-Gauthier, Isabelle; Odobel, Fabrice; Alebbi, Monica Inorganic Chemistry, Vol. 40, Issue 23 https://doi.org/10.1021/ic010192e	journal	November 2001
Note: Using fast digitizer acquisition and flexible resolution to enhance noise cancellation for high performance nanosecond transient absorbance spectroscopy Rimshaw, A.; Grieco, C.; Asbury, J. B. Review of Scientific Instruments, Vol. 86, Issue 6 https://doi.org/10.1063/1.4923093	journal	June 2015
Evidence for First-Order Charge Recombination in Dye-Sensitized Solar Cells Barr, Timothy J.; Meyer, Gerald J. ACS Energy Letters, Vol. 2, Issue 10 https://doi.org/10.1021/acsenergylett.7b00569	journal	September 2017
Transient Photovoltage Measurements in Nanocrystal-Based Solar Cells Lin, Weyde M. M.; Bozyigit, Deniz; Yarema, Olesya The Journal of Physical Chemistry C, Vol. 120, Issue 23 https://doi.org/10.1021/acs.jpcc.6b03695	journal	June 2016
Dynamics of Electron Recombination and Transport in Water-Splitting Dye-Sensitized Photoanodes Swierk, John R.; McCool, Nicholas S.; Mallouk, Thomas E. The Journal of Physical Chemistry C, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpcc.5b01442	journal	June 2015
Decreased Interfacial Charge Recombination Rate Constants with N3-Type Sensitizers Abrahamsson, Maria; Johansson, Patrik G.; Ardo, Shane The Journal of Physical Chemistry Letters, Vol. 1, Issue 11 https://doi.org/10.1021/jz100546y	journal	May 2010
Kinetic pathway for interfacial electron transfer from a semiconductor to a molecule Hu, Ke; Blair, Amber D.; Piechota, Eric J. Nature Chemistry, Vol. 8, Issue 9 https://doi.org/10.1038/nchem.2549	journal	June 2016
Self-assembled molecular p/n junctions for applications in dye-sensitized solar energy conversion Farnum, Byron H.; Wee, Kyung-Ryang; Meyer, Thomas J. Nature Chemistry, Vol. 8, Issue 9 https://doi.org/10.1038/nchem.2536	journal	June 2016
Evidence that Δ S ^‡ Controls Interfacial Electron Transfer Dynamics from Anatase TiO ₂ to Molecular Acceptors Troian-Gautier, Ludovic; DiMarco, Brian N.; Sampaio, Renato N. Journal of the American Chemical Society, Vol. 140, Issue 8 https://doi.org/10.1021/jacs.7b13243	journal	February 2018
Detailed comparison of the Williams–Watts and Cole–Davidson functions Lindsey, C. P.; Patterson, G. D. The Journal of Chemical Physics, Vol. 73, Issue 7 https://doi.org/10.1063/1.440530	journal	October 1980

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Title: Charge Recombination with Fractional Reaction Orders in Water-Splitting Dye-sensitized Photoelectrochemical Cells

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