David F. Watson

Influence of surface-attachment functionality on the aggregation, persistence, and electron-transfer reactivity of chalcogenorhodamine dyes on TiO2.

Chalcogenorhodamine dyes bearing phosphonic acids and carboxylic acids were compared as sensitizers of nanocrystalline TiO(2) in dye-sensitized solar cells (DSSCs). The dyes were constructed around a 3,6-bis(dimethylamino)chalcogenoxanthylium core and varied in the 9 substituent: 5-carboxythien-2-yl in dyes 1-E (E = O, Se), 4-carboxyphenyl in dyes 2-E (E = O, S), 5-phosphonothien-2-yl in dyes 3-E (E = O, Se), and 4-phosphonophenyl in dyes 4-E (E = O, Se). All dyes adsorbed to TiO(2) as mixtures of H aggregates and monomers, which exhibited broadened absorption spectra relative to those of purely amorphous monolayers. Surface coverages of dyes and the extent of H aggregation varied minimally with the surface-attachment functionality, the structure of the 9-aryl group, and the identity of the chalcogen heteroatom. Carboxylic acid-functionalized dyes 1-E and 2-E desorbed rapidly and completely from TiO(2) into acidified CH(3)CN, but phosphonic acid-functionalized dyes 3-E and 4-E persisted on TiO(2) for days. Short-circuit photocurrent action spectra of DSSCs corresponded closely to the absorptance spectra of dye-functionalized films; thus, H aggregation did not decrease the electron-injection yield or charge-collection efficiency. Maximum monochromatic incident photon-to-current efficiencies (IPCEs) of DSSCs ranged from 53 to 95% and were slightly higher for carboxylic acid-functionalized dyes 1-E and 2-E. Power-conversion efficiencies of DSSCs under white-light illumination were low (<1%), suggesting that dye regeneration was inefficient at high light intensities. The photoelectrochemical performance (under monochromatic or white-light illumination) of 1-E and 2-E decayed significantly within 20-80 min of the assembly of DSSCs, primarily because of the desorption of the dyes. In contrast, the performance of phosphonic acid-functionalized dyes remained stable or improved slightly on similar timescales. Thus, replacing carboxylic acids with phosphonic acids increased the inertness of chalcogenorhodamine-TiO(2) interfaces without greatly impacting the aggregation of dyes or the interfacial electron-transfer reactivity.

Attachment of CdSe Nanoparticles to TiO2 via Aqueous Linker-Assisted Assembly: Influence of Molecular Linkers on Electronic Properties and Interfacial Electron Transfer

CdSe nanoparticles (NPs) capped with cysteinate (Cys), 3-mercaptopropionate (MP), and mercaptosuccinate (MS) were adsorbed to TiO(2) from basic aqueous dispersions. Native capping groups served as molecular linkers to TiO(2). Thus, the materials-assembly chemistry was simplified and made more reproducible and environmentally benign. The electronic properties of CdSe and the electron-transfer reactivity at CdSe-linker-TiO(2) interfaces varied with the structure and functionality of the capping groups. Cys-capped CdSe NPs exhibited a narrow and intense first excitonic absorption band centered at 422 nm, suggesting that they were magic-sized nanocrystals (MSCs) with diameters less than 2 nm. MP- and MS-capped CdSe NPs had broader and lower-energy absorption bands, which are typical of regular quantum dots. Photocurrent action spectra of nanocrystalline TiO(2) films functionalized with Cys-CdSe, MP-CdSe, and MS-CdSe overlaid closely with absorption spectra, indicating that excitation of CdSe gave rise to the injection of electrons into TiO(2). Under white-light illumination, the global energy-conversion efficiency for Cys-capped CdSe ((0.45 ± 0.11)%) was 1.2-to-6-fold greater than for MP- and MS-capped CdSe. Similarly, the absorbed photon-to-current efficiency was 1.3-to-3.3-fold greater. These differences arose from linker-dependent variations of electron-injection and charge-recombination reactivity. Transient absorption measurements indicated that electron injection from Cys-capped CdSe was more efficient than from MS-capped CdSe. In addition, charge recombination at CdSe-MS-TiO(2) interfaces was complete within hundreds of nanoseconds, whereas the charge-separated-state lifetime at CdSe-Cys-TiO(2) interfaces was on the order of several microseconds. Thus, Cys-capped CdSe MSCs are readily attached to TiO(2) and exhibit unusual electronic properties and desirable electron-transfer reactivity.

Study on the Effects of Humic and Fulvic Acids on Quantum Dot Nanoparticles Using Capillary Electrophoresis with Laser-Induced Fluorescence Detection

The increasing production and use of quantum dot (QD) nanoparticles have caused concerns on the possibility of contaminating the aquatic and terrestrial ecosystems with wastes that may contain QDs. Therefore, studies on the behavior of QDs upon interaction with components of the natural environment have become of interest. This study investigated the fluorescence and electrophoretic mobility of carboxylic or amine polyethylene glycol (PEG)-functionalized CdSe/ZnS QDs in the presence of two aquatic humic substances (HS), Suwannee River humic and fulvic acids, using capillary electrophoresis with laser-induced fluorescence detection. Results showed initial enhancement in fluorescence of QDs at the onset of the interaction with HS, followed by fluorescence quenching at longer exposure with HS (>30 min). It was also observed that the electrophoretic mobility of QDs increases with increasing concentration of HS, suggesting an increase in the ratio in charge to hydrodynamic size of the nanoparticles. To determine if the QDs degraded upon interaction with HS, the QD-HS mixtures were dialyzed to separate free Cd2+ from intact QDs, followed by analysis of the solutions using inductively coupled plasma-mass spectrometry. Results suggested that degradation of QDs in the presence of HS did not occur within the period of incubation.

Differences in Soil Mobility and Degradability between Water-Dispersible CdSe and CdSe/ZnS Quantum Dots

The relative leaching potential and degradation of water-dispersible CdSe and CdSe/ZnS quantum dots (QDs) were evaluated using small-scale soil columns. The potential of QDs to release toxic Cd(2+) and/or Se(2-)/SeO(3)(2-) ions upon degradation is of environmental concern and warrants investigation. Both classes of QDs exhibited limited soil mobility in CaCl(2), with more than 70% of the total Cd and Se species from QDs retained in the top soil after passing 10 column volumes of solution through the soil column. However, mobilization of Cd- and Se-species was observed when EDTA was used as the leaching solution. Approximately 98% of the total Cd(2+) loaded leached out from the Cd(2+)-spiked soil, while only 30% and 60% leached out from the CdSe and CdSe/ZnS QD-spiked soils, respectively. Soil column profiles and analysis of leachates suggest that intact QDs leached through the soil. Longer incubation (15 days) in soil prior to leaching indicated some degradation and/or surface modification of both QDs. These results suggest that chelating agents in the environment can enhance the soil mobility of intact and degraded QDs. It is apparent that QDs in soil, including the polymer-coated CdSe/ZnS QDs that are generally assumed to possess a higher degree of environmental stability, can undergo chemical transformations, which subsequently dictate their overall mobility.

From seconds to femtoseconds: solar hydrogen production and transient absorption of chalcogenorhodamine dyes.

A series of chalcogenorhodamine dyes with oxygen, sulfur, and selenium atoms in the xanthylium core was synthesized and used as chromophores for solar hydrogen production with a platinized TiO2 catalyst. Solutions containing the selenorhodamine dye generate more hydrogen [181 turnover numbers (TONs) with respect to chromophore] than its sulfur (30 TONs) and oxygen (20 TONs) counterparts. This differs from previous work incorporating these dyes into dye-sensitized solar cells (DSSCs), where the oxygen- and selenium-containing species perform similarly. Ultrafast transient absorption spectroscopy revealed an ultrafast electron transfer under conditions for dye-sensitized solar cells and a slower electron transfer under conditions for hydrogen production, making the chromophores triplet yield an important parameter. The selenium-containing species is the only dye for which triplet state population is significant, which explains its superior activity in hydrogen evolution. The discrepancy in rates of electron transfer appears to be caused by the presence or absence of aggregation in the system, altering the coupling between the dye and TiO2. This finding demonstrates the importance of understanding the differences between, as well as the effects of the conditions for DSSCs and solar hydrogen production.

Aqueous-Phase Linker-Assisted Attachment of Cysteinate(2–)-Capped CdSe Quantum Dots to TiO2 for Quantum Dot-Sensitized Solar Cells

We have synthesized water-dispersible cysteinate(2-)-capped CdSe nanocrystals and attached them to TiO2 using one-step linker-assisted assembly. Room-temperature syntheses yielded CdSe magic-sized clusters (MSCs) exhibiting a narrow and intense first excitonic absorption band centered at 422 nm. Syntheses at 80 °C yielded regular CdSe quantum dots (RQDs) with broader and red-shifted first excitonic absorption bands. Cysteinate(2-)-capped CdSe MSCs and RQDs adsorbed to bare nanocrystalline TiO2 films from aqueous dispersions. CdSe-functionalized TiO2 films were incorporated into working electrodes of quantum dot-sensitized solar cells (QDSSCs). Short-circuit photocurrent action spectra of QDSSCs corresponded closely to absorptance spectra of CdSe-functionalized TiO2 films. Power-conversion efficiencies were (0.43±0.04)% for MSC-functionalized TiO2 and (0.83±0.11)% for RQD-functionalized TiO2. Absorbed photon-to-current efficiencies under white-light illumination were approximately 0.3 for both MSC- and RQD-based QDSSCs, despite the significant differences in the electronic properties of MSCs and RQDs. Cysteinate(2-) is an attractive capping group and ligand, as it engenders water-dispersibility of CdSe nanocrystals with a range of photophysical properties, enables facile all-aqueous linker-assisted attachment of nanocrystals to TiO2, and promotes efficient interfacial charge transfer.

Partitioning of hydrophobic CdSe quantum dots into aqueous dispersions of humic substances: Influence of capping-group functionality on the phase-transfer mechanism

Studies of the fate and transport of engineered nanomaterials are invaluable in predicting environmental impact, bioavailability, and toxicity. We report on the influence of humic and fulvic acids (models of natural organic matter) on the phase transfer of organic-capped CdSe quantum dots (QDs) from hexane to water. QDs capped with tri-n-octylphosphine oxide, tetradecylphosphonic acid, and oleic acid, which were otherwise insoluble in water, were transferred into aqueous solutions of humic substances (HS) (Suwannee River humic acid and fulvic acid standards) within 1-10 days after mixing. Phase transfer was characterized by infrared and UV/Vis absorption spectroscopy, emission spectroscopy, dynamic light scattering, electron microscopy, and inductively coupled plasma mass spectrometry. Phase-transferred QDs were intact and temporarily stabilized by HS. On longer timescales, Cd(2+) leached into aqueous solution. Our data suggest that two mechanisms promote the phase transfer of QD-HS agglomerates: (1) an overcoating mechanism involving dispersion interactions between non-polar moieties of HS and hydrocarbon chains of organic capping groups and (2) a coordinative mechanism involving displacement of capping groups by Lewis basic functionalities of HS. The structure of the capping group of QDs influenced the relative contributions of the two mechanisms and the extent to which Cd(2+) leached into water.

Selenorhodamine Dye-Sensitized Solar Cells: Influence of Structure and Surface-Anchoring Mode on Aggregation, Persistence, and Photoelectrochemical Performance

A library of six selenorhodamine dyes (4-Se-9-Se) were synthesized, characterized, and evaluated as photosensitizers of TiO2 in dye-sensitized solar cells (DSSCs). The dyes were constructed around either a bis(julolidyl)- or bis(half-julolidyl)-modified selenoxanthylium core functionalized at the 9-position with a thienyl group bearing a carboxylic, hydroxamic, or phosphonic acid for attachment to TiO2. Absorption bands of solvated dyes 4-Se-9-Se were red-shifted relative to the dimethylamino analogues. The dyes adsorbed to TiO2 as mixtures of monomeric and H-aggregated dyes, which exhibited broadened absorption spectra and increased light-harvesting efficiencies relative to the solvated monomeric dyes. Carboxylic acid-bearing dyes 4-Se and 7-Se initially exhibited the highest incident photon-to-current efficiencies (IPCEs) of 65-80% under monochromatic illumination, but the dyes desorbed rapidly from TiO2 into solutions of HCl (0.1 M) in a CH3CN:H2O mixed solvent (120:1 v:v). The hydroxamic acid- and phosphonic acid-bearing dyes 5-Se, 6-Se, 8-Se, and 9-Se exhibited lower IPCEs (49-65%) immediately after preparation of DSSCs; however, the dyes were vastly more inert on TiO2, and IPCEs decreased only minimally with successive measurements under constant illumination. Power-conversion efficiencies (PCEs) of the selenorhodamine-derived DSSCs were less than 1%, probably due to inefficient regeneration of the dyes following electron injection. For a given anchoring group, the bis(half-julolidyl) dyes exhibited higher open-circuit photovoltages and PCEs than the corresponding bis(julolidyl) dyes. The hydroxamic acid- and phosphonic acid-bearing dyes are intriguing photosensitizers of TiO2 in light of their aggregation-induced spectral broadening, high monochromatic IPCEs, and relative inertness to desorption into acidic media.

Influence of Solvation and the Structure of Adsorbates on the Kinetics and Mechanism of Dimerization-Induced Compositional Changes of Mixed Monolayers on TiO2

Mixed monolayers of thiol-terminated (T) and methyl-terminated (Me) carboxylic acids on nanocrystalline TiO(2) films underwent dimerization-induced compositional changes. At short reaction times, the compositions of mixed monolayers were kinetically controlled and mirrored the compositions of coadsorption solutions. On time scales up to several hours, well after the establishment of saturation surface coverages, the monolayers relaxed to thermodynamically controlled compositions through the displacement of Me by T. Equilibration was driven by the formation of intermolecular disulfide bonds between thiol groups of adsorbed T, which yielded polydentate dimeric adsorbates that were bound more strongly than monomeric adsorbates to TiO(2). The rate of compositional changes increased with decreasing solvent viscosity and decreasing alkyl chain length of T, suggesting that the rate of adsorption of T to TiO(2) strongly influenced the overall kinetics under certain conditions. Steric bulk within adsorbates and the strength of surface-attachment interactions also influenced the rate of compositional changes. A kinetic model, derived on the basis of Langmuir adsorption and desorption kinetics, accounts for key aspects of the mixed-monolayer compositional changes. The rate-determining step in the overall mechanism involved either the adsorption of T or the formation of disulfide bonds, depending on the conditions under which monolayers were prepared. Our findings illustrate that dimerization and other intermolecular interactions between adsorbates may dramatically influence the composition and terminal functionalization of mixed monolayers.

Linker-assisted attachment of CdSe quantum dots to TiO2: Time- and concentration-dependent adsorption, agglomeration, and sensitized photocurrent.

We have characterized the concentration and time dependences of the attachment of colloidal CdSe quantum dots (QDs) to 16-mercaptohexadanoic acid (MHDA)-functionalized nanocrystalline TiO2 thin films. The amount of QDs and the extent of their agglomeration on MHDA-functionalized TiO2 films were characterized by transmission- and reflectance-mode UV/vis absorption spectroscopy and scanning electron microscopy. Optically transparent films with spatially homogeneous coloration and minimal agglomeration of QDs were prepared from 2.2 and 5.0 μM toluene dispersions of QDs at short reaction times (<5 h). In contrast, prolonged exposure of MHDA-functionalized TiO2 films to 22 μM dispersions of QDs yielded relatively opaque QD-functionalized films with spatially inhomogeneous coloration and substantial agglomeration of QDs. Agglomeration of QDs decreased the absorbed photon-to-current efficiencies of QD-sensitized solar cells (QDSSCs) by almost 3-fold. These results highlight the profound influence of agglomeration on the optical properties and interfacial electron-transfer reactivity of QD-functionalized TiO2 films prepared by in situ linker-assisted assembly as well as the photoelectrochemical performance of QDSSCs incorporating such films.