Robert J. Dillon

Active facets on titanium(III)-doped TiO2: an effective strategy to improve the visible-light photocatalytic activity.

The properties and applications of materials are significantly controlled by their physical characteristics, such as size, shape, and structural state. Many processes are governed by interface reactions by which the surface energy and reactivity depend on the spatial configuration, coordination, and structural state of surface atoms and molecules. For crystals, this dependence is directly related to the expression of specific crystallographic faces, which exhibit different surface structures and atomic configurations. These differences explain why some applications, such as molecular adsorption and desorption, gas sensing, drug molecule delivery and release, and heterogeneous catalysis are highly sensitive to the surface atomic structures. Recent progress in the engineering of crystal morphology has included the synthesis of polyhedral silver nanocrystals by the polyol method, the epitaxially seeded growth of highly faceted Pt-Pd nanocrystals, and the controlled overgrowth of Pd-Au core–shell structures enclosed by {111} facets. Apart from these metallic nanocrystals, binary or ternary compounds with preferentially developed facets have also been reported. The facet effect is an important factor for heterogeneous photocatalysts, because surface atom arrangement and coordination intrinsically determine the adsorption of reactant molecules, surface transfer between photoexcited electrons and reactant molecules, and desorption of product molecules. This phenomenon has been well studied in TiO2 photocatalysts. TiO2 is one of the most extensively studied photocatalysts owing to its abundance, nontoxicity, and stability. However, for practical applications, pure TiO2 is not a good candidate because it is only active under ultraviolet (UV) irradiation owing to the band gap of 3.2 eV for the anatase phase. Therefore, band-gap engineering is required to use TiO2 as a water-splitting catalyst under visible-light irradiation. Reduced TiO2 (TiO2 x), containing Ti or O vacancies, has been reported to show visible-light absorption. Various strategies have been applied to synthesize reduced TiO2, such as heating under vacuum [8] or reducing gas, laser irradiation, and high-energy particle bombardment (electrons or Ar ions). A big challenge for the application of reduced TiO2 is that the surface oxygen defects are highly unstable in air owing to the susceptibility of Ti toward oxidation by O2. [13] Recently, we reported a facile one-step combustion method to synthesize partially reduced TiO2. [14] The presence of Ti in the sample extends the photoresponse of TiO2 from the UV to the visible light region, which leads to high visible-light photocatalytic activity for the generation of hydrogen gas from water. However, in the rapid and harsh combustion process, there is very limited control over the crystallization process, which results in the irregularly shaped products. Herein we report the development of a simple solution method to grow non-stoichiometric rutile TiO2 crystals with desired facets. The incorporation of Ti, which extends the light absorption from the UV into the visible range, along with the development of facets with high reactivity, results in a material exhibiting greatly enhanced photocatalytic H2 production activity relative to the combustion product we reported before. Powder X-ray diffraction analysis (Figure 1a) shows that the sample of as-produced TiO2 (sample S1) has rutile structure. All of the diffraction peaks can be assigned to

Different rates of singlet fission in monoclinic versus orthorhombic crystal forms of diphenylhexatriene.

The dynamics of singlet fission (SF) are studied in monoclinic and orthorhombic crystals of 1,6-diphenyl-1,3,5-hexatriene. Picosecond time-resolved fluorescence measurements and the presence of a strong magnetic field effect indicate that up to 90% of the initially excited singlets undergo SF in both forms. The initial SF and subsequent triplet pair dissociation rates are found to be more rapid in the monoclinic crystal by factors of 1.5 and 3.5, respectively. These results provide clear evidence that molecular organization affects the rates of triplet pair formation and separation, both important parameters for determining the ultimate utility of a SF material.

Singlet Fission: From Coherences to Kinetics.

Singlet fission, in which an initially excited singlet state spontaneously splits into a pair of triplet excitons, is a process that can potentially boost the efficiency of solar energy conversion. The separate electronic bands in organic semiconductors make them especially useful for dividing a high-energy singlet exciton into a pair of lower-energy triplet excitons. Recent experiments illustrate the role of spin coherence in fission, while kinetic models are used to describe how triplet and singlet states interact on longer time scales. Despite insights gained from recent experiments, the detailed structure and dynamics of the electronic states involved in the initial step of singlet fission remain active areas of investigation. On longer time scales, finding ways to efficiently harvest the triplet excitons will be an important challenge for making devices based on this phenomenon. A full understanding of singlet fission requires consideration of a sequence of photophysical events (decoherence, relaxation, and diffusion) occurring on different time scales.

Promotion of atomic hydrogen recombination as an alternative to electron trapping for the role of metals in the photocatalytic production of H2

Significance The use of catalysis assisted by light is a promising route to convert solar energy into chemical fuels such as H2. Photon absorption promotes electrons in semiconductor catalysts from the valence to the conduction band of those solids, and the excited electrons may be used to reduce protons in water to produce hydrogen gas. Unfortunately, those electrons tend to rapidly return to their ground state instead. The addition of metals has been shown to enhance photocatalytic activity, and that has been explained by their ability to trap the excited electrons and quench the electron–hole recombination process that neutralizes the photoexcitation. Here we challenge the validity of this model and provide an alternative explanation for the enhancement. A new thinking about this mechanism may result in new searches for appropriate cocatalysts. The production of hydrogen from water with semiconductor photocatalysts can be promoted by adding small amounts of metals to their surfaces. The resulting enhancement in photocatalytic activity is commonly attributed to a fast transfer of the excited electrons generated by photon absorption from the semiconductor to the metal, a step that prevents deexcitation back to the ground electronic state. Here we provide experimental evidence that suggests an alternative pathway that does not involve electron transfer to the metal but requires it to act as a catalyst for the recombination of the hydrogen atoms made via the reduction of protons on the surface of the semiconductor instead.

Electronic Energy Migration on Different Time Scales: Concentration Dependence of the Time-Resolved Anisotropy and Fluorescence Quenching of Lumogen Red in Poly(methyl methacrylate)

Electronic energy transfer plays an important role in many types of organic electronic devices. Forster-type theories of exciton diffusion provide a way to calculate diffusion constants and lengths, but their applicability to amorphous polymer systems must be evaluated. In this paper, the perylenediimide dye Lumogen Red in a poly(methyl methacrylate) host matrix is used to test theories of exciton motion over Lumogen Red concentrations (C(LR)s) ranging from 1 x 10(-4) to 5 x 10(-2) M. Two experimental quantities are measured. First, time-resolved anisotropy decays in films containing only Lumogen Red provide an estimate of the initial energy transfer rate from the photoexcited molecule. Second, the Lumogen Red lifetime decays in mixed systems where the dyes Malachite Green and Rhodamine 700 act as energy acceptors are measured to estimate the diffusive quenching of the exciton. From the anisotropy measurements, it is found that theory accurately predicts both the C(LR)(-2) concentration dependence of the polarization decay time tau(pol), as well as its magnitude to within 30%. The theory also predicts that the diffusive quenching rate is proportional to C(LR)(alpha), where alpha ranges between 1.00 and 1.33. Experimentally, it is found that alpha = 1.1 +/- 0.2 when Malachite Green is used as an acceptor, and alpha = 1.2 +/- 0.2 when Rhodamine 700 is the acceptor. On the basis of the theory that correctly describes the anisotropy data, the exciton diffusion constant is projected to be 4-9 nm(2)/ns. By use of several different analysis methods for the quenching data, the experimental diffusion constant is found to be in the range of 0.32-1.20 nm(2)/ns. Thus the theory successfully describes the early time anisotropy data but fails to quantitatively describe the quenching experiments which are sensitive to motion on longer time scales. The data are consistent with the idea that orientational and energetic disorder leads to a time-dependent exciton migration rate, suggesting that simple diffusion models cannot accurately describe exciton motion within this system.

FRET detection of proteins using fluorescently doped electrospun nanofibers and pattern recognition.

This paper reports the fabrication of solid-state nanofiber sensor arrays and their use for detection of multiple proteins using principal component analysis (PCA). Four cationic and anionic fluorescently embedded nanofibers are generated by an electrospinning method, yielding unique patterns of fluorescence change upon interaction with protein samples. Five metal and nonmetal containing proteins, i.e., hemoglobin, myoglobin, cytochrome c, BSA, and avidin, have been investigated; and the results show that distinct fluorescent patterns can be formed upon the addition of protein samples to the array of solid nanofiber substrates, allowing their unambiguous identification. The nanofiber films are highly repeatable with a batch-to-batch variation of approximately 5% and demonstrated outstanding reusability with less than a 15% loss of fluorescence intensity signal after 5 regenerations of test cycles. For a more practical visualization, a cluster map was generated using PCA of the change-in-fluorescence (ΔI) composite patterns, demonstrating the potential of the method for diagnostic applications.

Time-Resolved Studies of Charge Recombination in the Pyrene/TCNQ Charge-Transfer Crystal: Evidence for Tunneling

Previous studies of solid-state tetracyanobenzene-based donor-acceptor complexes showed that these materials were highly susceptible to both laser and mechanical damage that complicated the analysis of their electron-transfer kinetics. In this paper, we characterize the optical properties of a pyrene/tetracyanoquinodimethane charge-transfer crystal that is much more robust than the tetracyanobenzene compounds. This donor-acceptor complex has a charge-transfer absorption that extends into the near-infrared, rendering the crystal black. We use time-resolved fluorescence and diffuse reflectance transient absorption to study its dynamics after photoexcitation. We show that the initially excited charge-transfer state undergoes a rapid, monoexponential decay with a lifetime of 290 ps at room temperature. There is no evidence for any long-lived intermediate or dark states; therefore, this decay is attributed to charge recombination back to the ground state. Fluorescence lifetime measurements demonstrate that this process becomes temperature-independent below 60 K, indicative of a thermally activated tunneling mechanism. The subnanosecond charge recombination makes this low-band-gap donor-acceptor material a poor candidate for generating long-lived electron-hole pairs.

The Effects of Photochemical and Mechanical Damage on the Excited State Dynamics of Charge-Transfer Molecular Crystals Composed of Tetracyanobenzene and Aromatic Donor Molecules

Charge-transfer molecular crystals are structurally well-defined systems whose electron transfer dynamics can be studied using time-resolved spectroscopy. In this paper, five 1:1 complexes, consisting of 1,2,4,5-tetracyanobenzene as the electron acceptor and durene, 9-methylanthracene, naphthalene, phenanthrene, and pyrene as electron donors, are studied using time-resolved fluorescence and transient absorption in the diffuse reflectance geometry. Two different sample morphologies were studied: single crystals and powders prepared by pulverizing the crystals and diluting them with barium sulfate microparticles. Fluorescence lifetime and transient absorption measurements performed on the crystals and the powders yielded different results. The crystals typically exhibited long-lived monoexponential fluorescence decays, while the powders had shorter multiexponential decays. Exposure of both types of samples to high laser fluence was also shown to induce faster excited state decay dynamics as observed using fluorescence and diffuse reflectance. In addition to the more rapid decays, these molecular crystals exhibited relatively high photobleaching quantum yields on the order of 10(-4). Previous work that interpreted picosecond decays in the transient absorption as evidence for rapid recombination and charge dissociation should be re-evaluated based on the susceptibility of this class of compounds to mechanical and photochemical damage.

Template assisted synthesis of silica-coated molecular crystal nanorods: From hydrophobic to hydrophilic nanorods

We report a method for the preparation of silica-coated molecular crystal nanorods. A sol-gel method was used to make silica nanotubes inside anodized alumina templates. The nanotubes were then loaded with 9-anthracene carboxylic acid (9-AC) and solvent annealed to produce silica-coated organic nanorods. The core-shell structure was confirmed using electron microscopy, and the highly crystalline organic core was characterized using powder X-ray diffraction and transmission electron microscopy. The silica-coated 9-AC rods had much improved dispersal properties in aqueous solution, and were also able to undergo reversible bending under UV illumination, as observed previously for uncoated 9-AC rods. This work demonstrates that it is possible to make surface-coated molecular crystal nanorods that retain their useful functionalities.