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Robin Humphry-Baker

Publications and source records attributed to Robin Humphry-Baker.

10 recordsLinked to original sources

Pyrene fluorescence at air/sodium dodecyl sulfate solution interface.

The dependence of pyrene fluorescence spectra on the concentration of sodium dodecyl sulfate (SDS) was observed, where the solution was prepared from water saturated with pyrene. The values of the I(1)/I(3) ratio from the bulk solution and from the upper meniscus region in an optical cell were similar but decreased rapidly around the critical micelle concentration (cmc) of SDS, indicating that pyrene molecules preferred to be solubilized in the micelles having a lower dielectric constant. The fluorescence intensity of the excimer indicated the concentration of pyrene molecules at the air/solution interface or the surface activity of pyrene molecules. In addition, the intensity from the meniscus region is much larger than that from the bulk at the concentrations below the cmc, whereas there was no difference in the intensity between the bulk and the meniscus above 8 mmol dm(-3) of SDS. The analysis of the fluorescence intensity from the excimer strongly suggests the presence of molecular aggregates that are favorable to the pyrene molecules just like the micelles in the bulk, making them less movable.

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Molecular wiring of nanocrystals: NCS-enhanced cross-surface charge transfer in self-assembled Ru-complex monolayer on mesoscopic oxide films.

We report on rapid ambipolar cross-surface charge transfer within self-assembled monolayers (SAM) of the heteroleptic Ru-complexes cis-RuLL'(NCS)(2) (L = 2,2'-bipyridyl-4,4'-dicarboxylic acid, L' = 4,4'-dinonyl-2,2'-bipyridyl) (1) and cis-RuLL' '(NCS)(2) (L = 2,2'-bipyridyl-4,4'-dicarboxylic acid, L' = 4,4'-dimethyl-2,2'-bipyridyl) (2) on the surface of mesoscopic insulating oxide films. The bipyridyl ligands of the Ru-complex transport electrons, while the NCS groups plays a pivotal role in mediating surface confined hole percolation. Molecular dynamics calculations show the NCS ligands of 1 and 2 to orient in a fashion that enhances the overlap of the HOMOs of neighboring ruthenium complexes. Using ab initio Hartree-Fock calculations the electronic coupling matrix element for intermolecular hole exchange at the surface is estimated to be 0.13 eV. Cyclic voltammetry as well as spectroelectrochemical and impedance measurements performed with a series of other Ru-complexes confirmed the control of the cross surface charge transfer by the molecular structure. Complex 2 shows the highest percolation rate, the surface hole diffusion coefficient being 1.1 x 10(-8) cm(2)/s. The effects of the ligand properties, such as denticity, geometry, and size, on the intermolecular charge transport are discussed in detail.

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High molar extinction coefficient heteroleptic ruthenium complexes for thin film dye-sensitized solar cells.

Two novel heteroleptic sensitizers, Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-hexyloxystyryl)-2,2-bipyridine)(NCS)2 and Ru((4,4-dicarboxylic acid-2,2'-bipyridine)(4,4'-bis(p-methoxystyryl)-2,2'-bipyridine) (NCS)2, coded as K-19 and K-73, respectively, have been synthesized and characterized by 1H NMR, FTIR, UV-vis absorption, and emission spectroscopy and excited-state lifetime and spectroelectrochemical measurements. The introduction of the alkoxystyryl group extends the conjugation of the bipyridine donor ligand increasing markedly their molar extinction coefficient and solar light harvesting capacity. The dynamics of photoinduced charge separation following electronic excitation of the K-19 dye was scrutinized by time-resolved laser spectroscopy. The electron transfer from K-19 to the conduction band of TiO2 is completed within 20 fs while charge recombination has a half-life time of 800 s. The high extinction coefficients of these sensitizers enable realization of a new generation of a thin film dye sensitized solar cell (DSC) yielding high conversion efficiency at full sunlight even with viscous electrolytes based on ionic liquids or nonvolatile solvents. An unprecedented yield of over 9% was obtained under standard reporting conditions (simulated global air mass 1.5 sunlight at 1000 W/m2 intensity) when the K-73 sensitizer was combined with a nonvolatile "robust" electrolyte. The K-19 dye gave a conversion yield of 7.1% when used in conjunction with the binary ionic liquid electrolyte. These devices exhibit excellent stability under light soaking at 60 degrees C. The effect of the mesoscopic TiO2 film thickness on photovoltaic performance has been analyzed by electrochemical impedance spectroscopy (EIS).

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Ion coordinating sensitizer for high efficiency mesoscopic dye-sensitized solar cells: influence of lithium ions on the photovoltaic performance of liquid and solid-state cells.

A Li+ coordinating sensitizer, NaRu(4-carboxylic acid-4'-carboxylate)(4,4'-bis[(triethylene glycol methyl ether) methyl ether]-2,2'-bipyridine)(NCS)2 (coded as K51), has been synthesized, and the effect of Li+ coordination on its performance in mesoscopic titanium dioxide dye-sensitized solar cells has been investigated. Fourier transform infrared spectra suggest that Li+ coordinates to the triethylene oxide methyl ether side chains on the dye molecules. With the addition of Li+ to a nonvolatile liquid electrolyte, we observe a significant increase in the photocurrent density, with only a small decrease in the open-circuit voltage, contrary to a non ion coordinating dye which displays a large drop in potential with the addition of Li+. For a solar cell incorporating an organic hole-transporter, we find the potential rises with increasing the Li+ concentration in the hole-transporter matrix. For the liquid electrolyte and solid-state cells, we obtain power conversion efficiencies of 7.8% and 3.8%, respectively, under simulated sunlight.

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Influence of 4-guanidinobutyric acid as coadsorbent in reducing recombination in dye-sensitized solar cells.

Dye-sensitized solar cells based on nanocrystalline TiO(2) have been fabricated with an amphiphilic ruthenium sensitizer [Ru (4,4'-dicarboxylic acid-2,2'-bipyridine) (4,4'-bis(p-hexyloxystyryl)-2,2'-bipyridine)(NCS)(2)], coded as K-19, and 4-guanidinobutyric acid (GBA) as coadsorbent. The cells showed a approximately 50 mV increase in open-circuit voltage and a similar current in comparison with cells without GBA cografting. The performance of both types of devices was evaluated on the basis of their photocurrent-voltage characteristics, dark current measurements, cyclic voltammetry, electrochemical impedance spectroscopy, and phototransient decay methods. The results indicate that GBA shifted the conduction band of TiO(2) toward a more negative potential and reduced the interfacial charge-transfer reaction from conduction band electrons to triiodide in the electrolyte (also known as the back reaction). In addition, the devices with GBA cografting showed an excellent stability with a power conversion efficiency of approximately 8% under simulated full sunlight (air mass 1.5, 100 mW cm(-2)) during visible light soaking at 60 degrees C.

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Efficient light harvesting by using green Zn-porphyrin-sensitized nanocrystalline TiO2 films.

A series of novel zinc metalloporphyrins, cyano-3-(2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-acrylic acid (Zn-3), 3-(trans-2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-acrylic acid (Zn-5), 2-cyano-5-(2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-penta-2,4-dienoic acid (Zn-8), 4-(trans-2'-(2' '-(5' ',10' ',15' ',20' '-tetraphenylporphyrinato zinc(II))yl)ethen-1'-yl))-1,2-benzenedicarboxylic acid (Zn-11), and 2-cyano-3-[4'-(trans-2' '-(2' ''-(5' '',10' '',15' '',20' ''-tetraphenylporphyrinato zinc(II))yl) ethen-1' '-yl)-phenyl]-acrylic acid (Zn-13) were synthesized and characterized by using various spectroscopic techniques. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that key molecular orbitals (MOs) of porphyrins Zn-5 and Zn-3 are stabilized and extended out onto the substituent by pi-conjugation, causing enhancement and red shifts of visible transitions and increasing the possibility of electron transfer from the substituent. The porphyrins were investigated for conversion of sunlight into electricity by constructing dye-sensitized TiO(2) solar cells using an I(-)/I(3)(-) electrolyte. The cells yield close to 85% incident photon-to-current efficiencies (IPCEs), and under standard AM 1.5 sunlight, the Zn-3-sensitized solar cell demonstrates a short circuit photocurrent density of 13.0 +/- 0.5 mA/cm(2), an open-circuit voltage of 610 +/- 50 mV, and a fill factor of 0.70 +/- 0.03. This corresponds to an overall conversion efficiency of 5.6%, making it the most efficient porphyrin-sensitized solar cell reported to date.

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Charge separation and efficient light energy conversion in sensitized mesoscopic solar cells based on binary ionic liquids.

A 7.4% power conversion efficiency at air mass (AM) 1.5 full sunlight was reached with a mesoscopic solar cell employing a new binary ionic liquid electrolyte composed of 1-propyl-3-methylimidazolium iodide and 1-ethyl-3-methylimidazolium tricyanomethanide in conjunction with the amphiphilic ruthenium complex NaRu(4-carboxylic acid-4'-carboxylate)(4,4'-dinonyl-2,2'-bipyridine)(NCS)(2), coded as Z-907Na. Ultramicroelectrode voltammetric, nanosecond laser transient absorbance, and photovoltaic measurements show that a high iodide concentration is required for dye regeneration to compete efficiently with charge recombination. A surprisingly fast reductive quenching process is turned on in pure iodide melts. This channel is unproductive, explaining the lower photocurrents observed under these conditions.

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Cross surface ambipolar charge percolation in molecular triads on mesoscopic oxide films.

We report on cross surface ambipolar charge percolation within a monolayer of a molecular triad adsorbed on semiconducting or insulating mesoscopic metal oxide films. The triad consists of a triphenlyamine (TPA) donor and a perylenemonoimide (PMI) acceptor connected by a bithiophene (T2) bridge. The self-assembled PMI-T2-TPA monolayer exhibits p-type or n-type conduction depending on the potential that is applied to the conducting glass (FTO) electrode supporting the oxide films. Cross surface electron transfer is turned on at around -1.24 V (vs Fc+/Fc) where the PMI moiety is electroactive. The color of the film changes from red to blue during the reduction of the PMI. By contrast, lateral hole transfer is turned on at around 0.8 V (vs Fc+/Fc) where the TPA moiety becomes electroactive. The stepwise oxidation of the T2-TPA units at 0.79 and 1.28 V (vs Fc+/Fc) is associated with a color change of the film from red to black. Cyclic voltammetric as well as chronocoulometric and spectroelectrochemical measurements were applied to determine the percolation threshold for cross surface charge transfer and the diffusion coefficients for the electron and hole hopping process. The effect of oxide surface states on the lateral charge motion was also investigated.

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A solvent-free, SeCN-/(SeCN)3- based ionic liquid electrolyte for high-efficiency dye-sensitized nanocrystalline solar cells.

A solvent-free ionic liquid electrolyte based on the SeCN-/(SeCN)3- redox couple has been employed for high-efficiency dye-sensitized nanocrystalline solar cells. For the first time an alternative redox couple has been identified to rival and even exceed the performance of the iodide/triiodide couple even at full sunlight. Unprecedented 7.5-8.3% power conversion efficiencies under AM 1.5 sunlight have been achieved for photovoltaic devices with solvent-free ionic liquid electrolytes.

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