Synthesis of Oligomeric Ruthenium Polypyridyl Dyes for
Photoelectrochemical Cells
August J. Rothenberger, Chris L. Gray, and Thomas E. Mallouk
Department of Chemistry, The Pennsylvania State University, 16802
Introduction
• Photoelectrochemical (PEC) cells are an alternative to
photovoltaic cells (solar panels)
• Store energy as hydrogen instead of in batteries
• PEC cells split water using a dye, catalyst and TiO2
• Electron promotion at the anode of a PEC cell forms holes,
which can be used to oxidize water
2𝐻2 𝑂 + 4ℎ+ → 𝑂2 + 4𝐻+ + 4𝑒 −
• Displaced electrons in the conduction band move to the
cathode, where they are used to reduce protons to H2 gas
2𝐻+ + 2𝑒 − → 𝐻2
Figure 1. Electron energy transitions at the anode of a dye sensitized
water-splitting PEC cell
Hole Diffusion
• A hole is formed when light excites the dye
• Promoted electron transferred into conduction band of TiO2
• Hole is transferred to oxygen evolution reaction (OER) catalyst
• Oxygen evolution catalyst requires four holes to oxidize water
• Hole transport is limited by proximity of dye to catalyst
• Holes can also be transported from an excited dye to another
nearby dye molecule
• The oligomer forces dye molecules in close proximity to one another,
facilitating more efficient hole diffusion across the electrode surface
Figure 3. Electron/hole transport between dye molecules at the electrode surface
• Ruthenium polypyridyl dyes can be attached to TiO2 anodes,
allowing a PEC cell to absorb visible light
• Short chain oligomeric ruthenium dyes can be synthesized by
connecting dye molecules via covalent linkages
• Designed to improve hole diffusion across electrode
surface and long term stability
Research Goal: Increase efficiency of dye-sensitized PEC cells by
using oligomer to improve electron transport and dye stability
Dye Synthesis and Deposition
• Monomer is a phosphonated Ru(bipyridine)3 synthesized using
literature methods
• Novel oligomer synthesis links dye complexes via alkyl chains
• Incorporates a phosphonate anchor group
Figure 2. Chemical structure of the phosponated oligomeric dye
• Dyes deposited onto electrodes from solvent over 15h
• Anchor groups attach to TiO2 on electrode surface
• Electrodes should have dye monolayer, absent of aggregates
• Aggregates fluoresce, unable to transfer electrons to TiO2
Monomer Oligomer
Dapp = 5.67*10-7 Dapp = 5.57*10-7
Figure 4. Monomer and oligomer dye abs vs time on electrode
• Electrodes can be electrochemically oxidized to simulate
working conditions, bleaching the dye
• Upon removal of voltage, dye absorbance recovers
• Hole transport across an electrode can be quantified using Dapp,
the cross-surface electron diffusion constant
1/2
∆𝐴2 𝑑 2 𝜋 2𝐴𝑚𝑎𝑥 𝐷𝑎𝑝𝑝 𝑡 1/2
𝐷𝑎𝑝𝑝 = Δ𝐴 =
4∗𝐴2𝑚𝑎𝑥 𝑡 𝑑𝜋1/2
• Dye absorbance measured in 0.1M HClO4 at 490nm using a
1.5V bias versus Ag/AgCl reference
• Preliminary comparison of dyes shows inconclusive results
Long Term Stability
• Quantification of dye’s anchoring ability to electrode
• Electrodes are exposed to constant 450nm irradiation of
30mW/cm2 in acetate buffer with open circuit conditions
• Electrode absorbance measured as a function of time
• Radiation causes dye to be removed from electrode surface
and enter solution
• Oligomer is significantly more stable than monomer
• More anchor points per molecule allow the oligomer a
stronger hold on electrode
Oligomer
Monomer
Figure 5. Dye degradation as a function of time under illumination
Conclusions
• A phosphonated oligomeric ruthenium polypyridyl dye can be
synthesized by a novel route and deposited onto TiO2 film
• Oligomer performance is nearly equivalent to monomer in
hole diffusion experiment
• Oligomer is more strongly anchored to TiO2 film than
monomer and more stable under irradiation
Future Directions
• Determine influence of different solvents and perchlorate salts
on hole diffusion experiment
• Perform bulk electrolysis experiment to measure steady state
photocurrent capability of PEC cells constructed with oligomer
• Perform open circuit photovoltage experiment to measure
potential over PEC cells with oligomer
Acknowledgments
I would like to extend my gratitude to Chris Gray for mentoring
me throughout the project and Dr. Tom Mallouk for his guidance
and support. I would also like to thank Dr. Steve and Pat Benkovic
for funding my summer experience, the PSU Chemistry
Department for hosting me, and the US Department of Energy
under Contract DE-FG02-07ER15911.