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Papanikolas, John M.

Publications and source records attributed to Papanikolas, John M..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A quantitative model of charge injection by ruthenium chromophores connecting femtosecond to continuous irradiance conditions

A kinetic framework for the ultrafast photophysics of tris(2,2-bipyridine)ruthenium(II) phosphonated and methyl-phosphonated derivatives is used as a basis for modeling charge injection by ruthenium dyes into a semiconductor substrate. By including the effects of light scattering, dye diffusion, and adsorption kinetics during sample preparation and the optical response of oxidized dyes, quantitative agreement with multiple transient absorption datasets is achieved on timescales spanning femtoseconds to nanoseconds. In particular, quantitative agreement with important spectroscopic handles—the decay of an excited state absorption signal component associated with charge injection in the UV region of the spectrum and the dynamical redshift of a ~500 nm isosbestic point—validates our kinetic model. Pseudo-first-order rate coefficients for charge injection are estimated in this work, with an order of magnitude ranging from 10 11 to 10 12 s –1 . The model makes the minimalist assumption that all excited states of a particular dye have the same charge injection coefficient, an assumption that would benefit from additional theoretical and experimental exploration. Here, we have adapted this kinetic model to predict charge injection under continuous solar irradiation and find that as many as 68 electron transfer events per dye per second take place, significantly more than prior estimates in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ultrafast Relaxations in Ruthenium Polypyridyl Chromophores Determined by Stochastic Kinetics Simulations

Maximizing the efficiency of solar energy conversion using dye assemblies rests on understanding where the energy goes following absorption. Transient spectroscopies in solution are useful for this purpose, and the time-resolved data are usually analyzed with a sum of exponentials. This treatment assumes that dynamic events are well separated in time, and that the resulting exponential prefactors and phenomenological lifetimes are related directly to primary physical values. Such assumptions break down for coincident absorption, emission, and excited state relaxation that occur in transient absorption and photoluminescence of tris(2,2'-bipyridine)ruthenium(2+) derivatives, confounding the physical meaning of the reported lifetimes. Here, we use inductive modeling and stochastic chemical kinetics to develop a detailed description of the primary ultrafast photophysics in transient spectroscopies of a series of Ru dyes, as an alternative to sums of exponential analysis. Commonly invoked three-level schemes involving absorption, intersystem crossing (ISC), and slow nonradiative relaxation and incoherent emission to the ground state cannot reproduce the experimentally measured spectra. The kinetics simulations reveal that ultrafast decay from the singlet excited state manifold to the ground state competes with ISC to the triplet excited state, whose efficiency was determined to be less than unity. The populations predicted by the simulations are used to estimate the magnitudes of transition dipoles for excited state excitations and evaluate the influence of specific ligands. The mechanistic framework and methodology presented here are entirely general, applicable to other dye classes, and can be extended to include charge injection by molecules bound to semiconductor surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Enabling Efficient Creation of Long-Lived Charge-Separation on Dye-Sensitized NiO Photocathodes

The hole-injection and recombination photophysics for NiO sensitized with RuP ([Ru II (bpy) 2 (4,4'-(PO 3 H 2 ) 2 -bpy)] 2+ ) are explored. Ultrafast transient absorption (TA) measurements performed with an external electrochemical bias reflect the efficiency for productive hole-injection, that is, quenching of the dye excited state that results in a detectable charge-separated electron–hole pair, is linearly dependent on the electronic occupation of intragap states in the NiO film. Population of these states via a negative applied potential increases the efficiency from 0% to 100%. The results indicate the primary loss mechanism for dye-sensitized NiO is rapid nongeminate recombination enabled by the presence of latent holes in the surface of the NiO film. Our results indicate a new design paradigm for NiO photocathodes and devices centered on the avoidance of this recombination pathway.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Completing a Charge Transport Chain for Artificial Photosynthesis

A ruthenium polypyridyl chromophore with electronically isolated triarylamine substituents has been synthesized that models the role of tyrosine in the electron transport chain in photosystem II. When bound to the surface of a TiO 2 electrode, electron injection from a Ru(II) Metal-to-Ligand Charge Transfer (MLCT) excited state occurs from the complex to the electrode to give Ru(III). Subsequent rapid electron transfer from the pendant triarylamine to Ru(III) occurs with an observed rate constant of ~10 10 s –1 , which is limited by the rate of electron injection into the semiconductor. Finally, transfer of the oxidative equivalent away from the semiconductor surface results in dramatically reduced rates of back electron transfer, and a long-lived ($τ$ = ~165 μs) triarylamine radical cation that has been used to oxidize hydroquinone to quinone in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Pathways Following Electron Injection: Medium Effects and Cross-Surface Electron Transfer in a Ruthenium-Based, Chromophore–Catalyst Assembly on TiO 2

Interfacial dynamics following photoexcitation of the water oxidation assembly [((PO 3 H 2 ) 2 bpy) 2 Ru II (bpy-bimpy)Ru II (tpy)(OH 2 )] 4+ , -[Ru a II –Ru b II –OH 2 ] 4+ , on nanocrystalline TiO 2 electrodes, starting from either -[Ru a II –Ru b II –OH 2 ] 4+ or -[Ru a II –Ru b III –OH 2 ] 5+ , have been investigated. Transient absorption measurements for TiO 2 –[Ru a II –Ru b II –OH 2 ] 4+ in 0.1 M HPF 6 or neat trifluoroethanol reveal that electron injection occurs with high efficiency but that hole transfer to the catalyst, which occurs on the electrochemical time scale, is inhibited by local environmental effects. Back electron transfer occurs to the oxidized chromophore on the microsecond time scale. Photoexcitation of the once-oxidized assembly, TiO 2 –[Ru a II –Ru b III –OH 2 ] 5+ , in a variety of media, generates -[Ru a III –Ru b III –OH 2 ] 6+ . The injected electron randomly migrates through the surface oxide structure reducing an unreacted -[Ru a II –Ru b III –OH 2 ] 5+ assembly to -[Ru a II –Ru b II –OH 2 ] 4+ . In a parallel reaction, -[Ru a III –Ru b III –OH 2 ] 6+ formed by electron injection undergoes proton loss giving -[Ru a II –Ru b IV $=$O] 4+ with possible conversion to -[Ru a II –Ru b II –OH 2 ] 4+ by an electrolyte-mediated reaction. In the following slow step, re-equilibration on the surface occurs either by reaction with added Fe III/II or by cross-surface electron transfer between spatially separated -[Ru a II –Ru b IV $=$O] 4+ and -[Ru a II –Ru b II –OH 2 ] 4+ assemblies to give -[Ru a II –Ru b III –OH 2 ] 5+ with a half-time of t 1/2 ~ 68 μs. Finally, these results and analyses show that the transient surface behavior of the assembly and cross-surface reactions play important roles in producing and storing redox equivalents on the surface that are used for water oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Chromophore-Catalyst Assembly for Water Oxidation Prepared by Atomic Layer Deposition

Visible-light-driven water splitting was explored in a dye sensitized photoelectrosynthesis cell (DSPEC) based on a photoanode with a phosphonic acid-derivatized donor–π–acceptor (D–π–A) organic chromophore, 1, and the water oxidation catalyst [Ru(bda)(4-O(CH 2 ) 3 P(O 3 H 2 ) 2 -pyr)2], 2, (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate). The photoanode was prepared by using a layering strategy beginning with the organic dye anchored to an FTO|core/shell electrode, atomic layer deposition (ALD) of a thin layer (<1 nm) of TiO 2 , and catalyst binding through phosphonate linkage to the TiO 2 layer. Device performance was evaluated by photocurrent measurements for core/shell photoanodes, with either SnO 2 or nanoITO core materials, in acetate-buffered, aqueous solutions at pH 4.6 or 5.7. The absolute magnitudes of photocurrent changes with the core material, TiO 2 spacer layer thickness, or pH, observed photocurrents were 2.5-fold higher in the presence of catalyst. The findings of transient absorption measurements and DFT calculations reflect that electron injection by the photoexcited organic dye is ultrafast promoted by electronic interactions enabled by orientation of the dye’s molecular orbitals on the electrode surface. Rapid injection is followed by recombination with the oxidized dye which is 95% complete by 1.5 ns. While chromophore decomposition limits the efficiency of the DSPEC devices toward O 2 production, the flexibility of the strategy presented here offers a new approach to photoanode design.

14 SOLAR ENERGY↗
DOE OSTI2017

Interfacial Dynamics within an Organic Chromophore-Based Water Oxidation Molecular Assembly

Photoinduced electron injection, intra-assembly electron transfer, and back-electron transfer are investigated in a single-site molecular assembly formed by covalently linking a phosphonated terthiophene (T 3 ) chromophore to a Ru(terpyridine)(bipyridine)(L) 2+ (L = MeCN or H 2 O) water oxidation catalyst adsorbed onto a mesoporous metal-oxide (MO x ) film. Density functional theory calculations of the T 3 -trpy-Ru-L assembly indicate that the molecular components are strongly coupled with enhanced low-energy absorptions owing to the presence of an intraligand charge transfer (ILCT) transition between the T 3 and trpy moieties. Ultrafast spectroscopy of the MO x //T 3 -trpy-Ru-L assemblies reveals that excitation of the surface-bound T 3 chromophore results in ps–ns electron injection into the metal-oxide conduction band. Electron injection is followed by rapid (<35 ps) intra-assembly electron transfer from the Ru II catalyst to regenerate the T 3 chromophore with subsequent back-electron transfer on the microsecond time scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ultrafast recombination dynamics in dye-sensitized SnO 2 /TiO 2 core/shell films

In dye-sensitized photoelectrosynthesis cells (DSPECs), molecular chromophores and catalysts are integrated on a semiconductor surface to perform water oxidation or CO 2 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 SnO 2 /TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([RuII(bpy)2(4,4'-(PO 3 H 2 ) 2 bpy)] 2+ , RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 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 SnO 2 core and must tunnel through the TiO 2 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.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2016

Direct observation of light-driven, concerted electron–proton transfer

Significance Concerted proton-coupled electron transfer (EPT) reactions in which both electrons and protons transfer in tandem are at the heart of many chemical and biological conversions including photosystem II. We report here the direct observation of absorption bands arising from photoEPT transitions, in this case, in H-bonded complexes between N -methyl-4,4′-bipyridinium cation and biologically relevant donors including tyrosine. The importance of these observations follows from the earlier experimental observations by Taube and coworkers on intervalence transfer in mixed-valence complexes. The observation of these photoEPT transitions and the appearance of reactive radical products also points to a possible, if inefficient, role in DNA photodamage and, possibly, in the formation of reactive oxygen intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Role of Macromolecular Structure in the Ultrafast Energy and Electron Transfer Dynamics of a Light-Harvesting Polymer

Ultrafast energy and electron transfer (EnT and ET, respectively) are characterized in a light-harvesting assembly based on a π-conjugated polymer (poly(fluorene)) functionalized with broadly absorbing pendant organic isoindigo (iI) chromophores using a combination of femtosecond transient absorption spectroscopy and large-scale computer simulation. Photoexcitation of the π-conjugated polymer leads to near-unity quenching of the excitation through a combination of EnT and ET to the iI pendants. The excited pendants formed by EnT rapidly relax within 30 ps, whereas recombination of the charge-separated state formed following ET occurs within 1200 ps. A computer model of the excited-state processes is developed by combining all-atom molecular dynamics simulations, which provides a molecular-level view of the assembly structure, with a kinetic model that accounts for the multiple excited-state quenching pathways. In conclusion, direct comparison of the simulations with experimental data reveals that the underlying structure has a dramatic effect on the partitioning between EnT and ET in the polymer assembly, where the distance and orientation of the pendants in relation to the backbone serve to direct the dominant quenching pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗