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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Stable Iridium(IV) Complexes of an Oxidation-Resistant Pyridine-Alkoxide Ligand: Highly Divergent Redox Properties Depending on the Isomeric Form Adopted

The preparation of the facial and meridional isomers of [Ir( pyalk ) 3 ] ( pyalk = 2-(2-pyridyl)isopropanoate), as model complexes for a powerful water oxidation catalyst, is reported herein. The strongly donating N 3 O 3 ligand set is very oxidation-resistant, yet promotes facile metal-centered oxidation to form stable Ir(IV) compounds. The Ir III/IV reduction potentials of the two isomers differ by 340 mV despite the identical ligand set. A ligand field rationalization is advanced and supported by DFT calculations.

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DOE OSTI2016

Photocatalytic Conversion of Nitrobenzene to Aniline through Sequential Proton-Coupled One-Electron Transfers from a Cadmium Sulfide Quantum Dot

This paper describes the use of cadmium sulfide quantum dots (CdS QDs) as visible-light photocatalysts for the reduction of nitrobenzene to aniline through six sequential photoinduced, proton-coupled electron transfers. At pH 3.6–4.3, the internal quantum yield of photons-to-reducing electrons is 37.1% over 54 h of illumination, with no apparent decrease in catalyst activity. Monitoring of the QD exciton by transient absorption reveals that, for each step in the catalytic cycle, the sacrificial reductant, 3-mercaptopropionic acid, scavenges the excitonic hole in ~5 ps to form QD •– ; electron transfer to nitrobenzene or the intermediates nitrosobenzene and phenylhydroxylamine then occurs on the nanosecond time scale. The rate constants for the single-electron transfer reactions are correlated with the driving forces for the corresponding proton-coupled electron transfers. This result suggests, but does not prove, that electron transfer, not proton transfer, is rate-limiting for these reactions. Furthermore, nuclear magnetic resonance analysis of the QD–molecule systems shows that the photoproduct aniline, left unprotonated, serves as a poison for the QD catalyst by adsorbing to its surface. Performing the reaction at an acidic pH not only encourages aniline to desorb but also increases the probability of protonated intermediates; the latter effect probably ensures that recruitment of protons is not rate-limiting.

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DOE OSTI2015

A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment

Herein we describe facial and meridional isomers of [Rh III (pyalk) 3 ], as well as meridional [Rh IV (pyalk) 3 ] + {pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible Rh III/IV redox couple and to have a stable Rh(IV) form, which we characterize by EPR and UV–visible spectroscopy as well as X-ray crystallography. The unprecedented stability of the Rh(IV) species is ascribed to the exceptional donor strength of the ligands, their oxidation resistance, and the meridional coordination geometry.

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DOE OSTI2016

Ultrafast Two-Electron Transfer in a CdS Quantum Dot–Extended-Viologen Cyclophane Complex

Time-resolved optical spectroscopies revealmulti-electron transfer from the biexcitonic state of a CdS quantum dot toan adsorbed tetracationic compoundcyclobis(4,4'-(1,4-phenylene)bipyridin-1-ium-1,4-phenylene-bis(methylene))(ExBox 4+ )to formboth the ExBox 3+ ∙and the doubly reduced ExBox2(+∙)statesfrom a single laser pulse. Electron transfer in the single-exciton regime occurs in 1 ps.At higher excitation powers the second electron transfertakes~5ps, which leadsto a mixture of redox states of the acceptor ligand.The doubly reducedExBox2(+∙)state has a lifetime of ~10 ns, while CdS + ∙:ExBox 3+ ∙recombines with multiple time constants, the longest of which is ~300 μs. The long-lived charge separation and ability to accumulate multiple charges on ExBox 4+ demonstrate the potential of the CdS:ExBox4+complex to serve as a platform for two-electron photocataly-sis.

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DOE OSTI2016

Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy

The solution structures of highly active Ir water-oxidation catalysts are elucidated herein by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by 1 H and 17 O NMR, EPR, resonance Raman and UV–vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

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DOE OSTI2016

Extended-Charge-Transfer Excitons in Crystalline Supramolecular Photocatalytic Scaffolds

Coupling among chromophores in molecular assemblies is responsible for phenomena such as resonant energy transfer and intermolecular charge transfer. These processes are central to the fields of organic photovoltaics and photocatalysis, where it is necessary to funnel energy or charge to specific regions within the system. As such, a fundamental understanding of these transport processes is essential for developing new materials for photovoltaic and photocatalytic applications. Recently, photocatalytic systems based on photosensitizing perylene monomimide (PMI) chromophore amphiphiles were found to show variation in hydrogen gas (H 2 ) production as a function of nanostructure crystallinity. The 2D crystalline systems form in aqueous electrolyte solution, which provides a high dielectric environment where the Coulomb potential between charges is mitigated. This results in relatively weakly bound excitons that are ideal for reducing protons. Furthermore, in order to understand how variations in crystalline structure affect H 2 generation, two representative PMI systems are investigated theoretically using a modified Holstein Hamiltonian. The Hamiltonian includes both molecular Frenkel excitations (FE) and charge-transfer excitations (CTE) coupled nonadiabatically to local intramolecular vibrations. Signatures of FE/CTE mixing and the extent of electron/hole separation are identified in the optical absorption spectrum and are found to correlate strongly to the observed H 2 production rates. The absorption spectral signatures are found to sensitively depend on the relative phase between the electron and hole transfer integrals, as well as the diabatic energy difference between the Frenkel and CT exciton bands. Our analysis provides design rules for artificial photosynthetic systems based on organic chromophore arrays.

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DOE OSTI2016

Direct Observation of a Charge-Transfer State Preceding High-Yield Singlet Fission in Terrylenediimide Thin Films

Singlet exciton fission (SF) in organic chromophore assemblies results in the conversion of one singlet exciton (S 1 ) into two triplet excitons (T 1 ), provided that the overall process is exoergic, i.e., E (S 1 ) > 2 E (T 1 ). In this paper, we report on SF in thin polycrystalline films of two terrylene-3,4:11,12-bis(dicarboximide) (TDI) derivatives 1 and 2 , which crystallize into two distinct π-stacked structures. Femtosecond transient absorption spectroscopy (fsTA) reveals a charge-transfer state preceding a 190% T 1 yield in films of 1 , where the π-stacked TDI molecules are rotated by 23° along an axis perpendicular to their π systems. In contrast, when the TDI molecules are slip-stacked along their N–N axes in films of 2 , fsTA shows excimer formation, followed by a 50% T 1 yield.

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DOE OSTI2016

Influence of Anion Delocalization on Electron Transfer in a Covalent Porphyrin Donor–Perylenediimide Dimer Acceptor System

Photodriven electron transfer from a donor excited state to an assembly of electronically coupled acceptors has been proposed to enhance charge transfer efficiency in functional organic electronic materials. However, the circumstances under which this may occur are difficult to investigate in a controlled manner in disordered donor–acceptor materials. Here we investigate the effects of anion delocalization on electron transfer using zinc meso-tetraphenylporphyrin (ZnTPP) as a donor and a perylene-3,4:9,10-bis(dicarboximide) dimer as the acceptor (PDI 2 ). The PDI units of the dimer are positioned in a cofacial orientation relative to one another by attachment of the imide group of each PDI to the 4- and 5-positions of a xanthene spacer. Furthermore, the distal imide group of one PDI is linked to the para-position of one ZnTPP phenyl group to yield ZnTPP-PDI 2 . The data for the dimer are compared to two different ZnTPP-PDI monomer reference systems designed to probe electron transfer to each of the individual PDI molecules comprising PDI 2 . The electron transfer rate from the ZnTPP lowest excited singlet state to PDI 2 is increased by 50% relative to that in ZnTPP-PDI, when the data are corrected for the statistics of having two electron acceptors. Femtosecond transient IR absorption spectroscopy provides evidence that the observed enhancement in charge separation results from electron transfer producing a delocalized PDI 2 anion.

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