Carbon dioxide is the major greenhouse gas that is a bi-product of industrial approaches to energy production. Forests and nonagricultural lands act as a natural sink for CO2 removal from the atmosphere; however, the amount of emitted CO2 is significantly larger than the capacity of these natural sinks. This is particularly problematic as two cornerstones of our modern world, electricity generation and transportation, hold the largest share in greenhouse gas (such as CO2) emission. This leads to malignant impacts on the natural environment and human life, such as global warming. The obvious approach to reduce the amount of generated CO2 is to limit the use of fossil fuels. However, coal-fired power plants remain the largest source of electricity generation in 2014 and an equally potent and financially reasonable source is yet to be fully developed. Hence, new systems and strategies are crucial for the remediation of CO2. In this work, we present novel TiO2 nanoparticles, synthesized via a facile solution-phase method, which show a significant visible light absorption. The synthesized nanoparticles can be applied towards photoreduction of CO2 for hydrocarbon solar fuels production. A thorough photoemission spectroscopy analysis outlined the energy structure of the materials which uncovered a sub-bandgap absorption in the visible range due to the presence of intragap states. The origins of intragap states were investigated in greater detail using various characterization techniques. An in-depth chemical composition study of the developed material using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) indicated that the synthesized material is considerably un-doped. Further structural analysis using transmission electron microscopy (TEM) showed that distances between visible lattice fringes are matched with ordered crystalline phases of TiO2. The core emission study using XPS revealed that the oxygen vacancy defects in the structure--i.e. likely due the synthesis--are responsible for intragap states formation. Charge dynamics were investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. EPR spectra were dominated by signals from oxygen-centered surface hole trapping sites with principle g values [2.003, 2.010, 2.023]--i.e. Ti4+ ˗ O2- on anatase. A faint signal was also observed as a function of visible light illumination at 5 K with principle g value of 1.975 that is suggestive of Ti3+ in rutile, a typical product of UV light exposure. In general, this study demonstrates the potential of a relatively inexpensive material for photoreduction of CO2 and generation of solar fuels.

Nanomedicine is fostering significant advances in the development of platforms for early detection and treatment of diseases. Nanoparticles (NPs) like quantum dots (QDs) exhibit size-dependent optical properties for light-driven technologies, which might become important in bio-imaging, sensing and photo-dynamic therapy (PDT) applications. The present research addresses the synthesis of water-stable Cd-based QDs via a Microwave-Assisted synthesis approach using cadmium sulfate salt, and thioglycolic acid as Cd- and S-precursors, respectively. Selenide ions were available by reductive leaching of metallic Selenium in Sodium bisulfite solution. The size control and the tunability of the optical properties were achieved by a suitable control of the reaction temperature (in the 140°C- 190°C range) and reaction time (10 minutes-40 minutes). X-ray diffraction analyses suggested the development of a CdSe,S face cubic centered structure; the broadening of the diffraction peaks indicated the presence of very small nanocrystals in the samples. The average crystallite size was estimated at 5.50 nm ± 1.17nm and 3.72 nm ± 0.04 nm, for nanoparticles synthesized at 180°C after 40 minutes or 10 minutes of reaction, respectively. HRTEM images confirmed the crystalline nature and the small size of the synthesized nanocrystals. In turn, the exciton was red-shifted from 461nm to 549 nm when the reaction temperature was prolonged from 140°C to 190 °C, suggesting the crystal growth. The corresponding band gap values were approximately 2.2 eV, confirming the quantum confinement effect (bulk value 1.74eV). This red shift was also evidenced in PL measurements where the main emission peak was shifted from 507 nm to 564 nm when the samples were excited at 420 nm. A narrow size-tunable emission also was supported by the full width at half maximum (∼ 45 nm) for the synthesized nanocrystals. The reactive oxygen species generation capability of as-synthesized QDs was also investigated. The correlation between the particle size and the generation of (ROS) by the degradation of methylene blue was evident with a reduction of MB concentration from 10μM to 7.5μM and 6.7μM after 15 minutes of UV irradiation for reaction time of 10 min. and 40 min. respectively. No additional degradation was noticed after 60 minutes of irradiation.

The band gap energy of the TiO2 photocatalytic is high at 3.2 eV. Ultraviolet (UV) light irradiation (<388nm) is required for the photocatalytic application. The lowering the band gap energy of TiO2 and enlarging light absorbing area are effective ways to enhance the efficiency of photocatalytic activity. Furthermore, the morphology and crystal structure of nanosized TiO2 considerably influences its photocatalytic behavior.

In this study, sodium titanate nanorods were formed using an alkali-treatment and were heat treated at different temperatures. The photoelectrochemical properties of sodium titanate nanorods was measured as a function of heat treatment temperature. The nanorods were prepared on the surface of Ti disk with a diameter of 15mm and a thickness of 3mm. Ti disk was immersed in 5 M NaOH aqueous solution at a temperature of 60 °C for 24 h. Morphology of sodium titanate nanorods was observed using FE-SEM. Crystal structure of sodium titanate nanorods was analyzed using X-ray diffractometer. Photoluminescence (PL) and electrochemical impedance spectroscopy (EIS) was used to evaluate photoelectrochemical properties of sodium titanate nanorods. The thin amorphous sodium titanate layer was formed during alkali-treatment. The sodium titanate layer was changed to nanorods after heat treatment at a temperature of 700 °C. The thickness and length of sodium titanate nanorods obtained at 700 °C were around 100 nm and 1μm, respectively. The crystal structure of sodium titanate was identified with Na2Ti6O13. Above 900 °C, the morphology of nanorods changed to agglomerated shape and the thickness of nanorods increased to 1 μm. The lowest value of PL was obtained at a temperature of 700 °C, while nonalkali treated specimen showed the highest value of PL. EIS revealed that polarization resistance at interface between sodium titanate nanorods and electrolyte was increased with increasing heat treatment temperature.

A series of fluorine appended highly conjugated fullerenes were prepared containing fluoro-α-cyanostilbene and aryl ester units. These modified PCBM dyads are fully characterized by NMR, Mass spectrometry, UV-vis, and cyclic voltammetry (Figures 1-4). It was found that the presence of fluoro-α-cyanostilbenes and esters affects the cyclic voltammetry and absorption in the UV-Vis region. The PCBA modified fullerenes significantly influences the HOMO-LUMO energy and wide absorption compared to PCBM.

Photodynamic therapy (PDT) is an alternative to traditional cancer treatments. This approach involves the use of photosensitizer (PS) agents and their interaction with light. As a consequence, cytotoxic reactive oxygen species (ROS) are generated that, in turn will destroy tumors. On the other hand, ZnO is a biocompatible, nontoxic, and biodegradable material with the capability to generate ROS, specifically singlet oxygen (SO), which makes this material a promising candidate for 2-photon PDT. Doping ZnO with Li species is expected to induce defects in the host oxide structure that favors the formation of trap states that should affect the electronic transitions related to the generation of SO. The present work reports the effect of the level of Li-doping on the ZnO structure and its capability to generate SO. Li-doped ZnO nanoparticles were synthesized under size-controlled conditions using a modified version of the polyol method. XRD measurements confirmed the development of well-crystallized ZnO Wurtzite; the average crystallite sizes ranged between 13.3nm and 14.2 nm, with an increase in Li content. The corresponding band gap energy values, estimated from UV-vis measurements, decreased from 3.33 to 3.25 eV. Photoluminescence (PL) measurements of Li-ZnO revealed the presence of emission peaks centered on 363nm, 390nm, and 556 nm; these emission peaks correspond to the exciton emission, transition of shallow donor levels near of the conduction band to valence band such as interstitial Zn, and oxygen vacancies, respectively. The observed increase of the emission intensity of the 390 nm emission peak, relative to the intensity of the main emission peak at 363nm, was attributed to the promote of trap states due to interstitial Zn or Li-incorporation into the host oxide lattice. SO measurements evidenced the enhancing effect of the Li concentration on the capability of the doped ZnO to generate this species. This Li-dependence of SO generation can be attributed to the enhancement of the concentration of trap states in the host ZnO, as suggested by PL measurements. Accordingly, Li-ZnO would become cytotoxic to cancer cells via photo-induced ROS generation enabling this nanomaterial to be considered as a potential direct PS agent for the 2-photon PDT route.

We report the synthesis of Cu2SnS3 (CTS) nanostructures and its incorporation into an inorganic-organic hybrid device to enhance the photoresponse under AM 1.5 G solar illumination. The nanostructures were structurally and optically characterized. From X-ray diffraction (XRD) and Transmission electron microscopy (TEM) the CTS nanocrystals were found to be tetragonal. Flower like structures of CTS were obtained as seen from Scanning electron microscopy (SEM). A band gap of 1.4 eV was obtained from absorption studies. Two devices have been studied, P3HT: PCBM = 1: 1 and CTS: P3HT: PCBM = 8:1:1. The photocurrent increased from a value of 2.33 mA at dark to 2.5 mA for the P3HT-PCBM blend to 3.36 mA for CTS: P3HT: PCBM = 8:1:1 device. The responsivity, sensitivity, external quantum efficiency and specific detectivity increased from 18.81 mA/W, 1.07, 4.25% and 6.88 × 108 Jones respectively for P3HT:PCBM sample to 189.97 mA/W, 1.44, 42.9% and 6.95 × 109 Jones for CTS: P3HT: PCBM = 8:1:1 sample at 1V bias and 1 Sun illumination intensity. The time dependent photoresponse was stable over different ON-OFF cycles. From the fit to the rise and decay curves, the rise and decay time constants were obtained.

Nanoparticles (NPs) of Indium Antimonide (InSb) were synthesized using a vapor phase synthesis technique known as Inert Gas Condensation. NPs were directly deposited, at room temperature and under high vacuum, on glass cover slides, TEM grid, 1 inch-square (111) p-type Silicon wafer and Sodium Chloride substrates. XRD study revealed the crystalline behavior of these NPs exhibiting a cubic symmetry with preferred growth direction of (111). The average grain size of the NPs obtained using XRD results and the Debye-Scherrer formula was 25.62 nm. TEM studies showed a bimodal distribution of NPs with average NPs size of 13.70 and 33.20 nm. These values are consistent with the value obtained using XRD. 1:1 composition ratio of In:Sb was confirmed by the Energy Dispersive X-Ray Spectroscopy studies. The band gap of the NPs obtained using Fourier Transform Infrared (FTIR) spectroscopy was 0.413 eV at 300 K, which indicates quantum confinement in the band structure of these NPs.

A completely solid state dye sensitized solar cell (DSSSC) is proposed in which chemically robust phthalocyanine (Pc) sensitizers, F16ZnPc and F40ZnPc, are sandwiched between n-TiO2 and p-NiO. While the energy conversion efficiencies of conventional Grätzel cells are continually increasing, the DSSSC design effectively solves the long term stability issues of the volatile liquid electrolyte. Through analysis of the electronic structure of the Pc|semiconductor systems, the free energy associated with hole injection into the valence band of NiO upon photoexcitation of the sensitizer and electron injection into the conduction band of TiO2 from the reduced form of the sensitizer as well as the competing charge recombination processes are calculated. Thermodynamically, the charge injection processes are found to be favored over the undesired charge recombination processes. These findings suggest promising energy conversion for the NiO|Pc|TiO2 DSSSC.

Due to the potential applications to high-efficiency and light-weight solar cells, the growth of CuInGaSe2 (CIGS) nanoparticles is a recent research focus. We have developed a relatively simple solvothermal route to grow high quality CIGS nanoparticles in an autoclave under different temperatures (170 – 280°C). The effect of reaction temperature on the shape of CIGS nanoparticles has been investigated. At lower temperatures, the CIGS particles show plate-like shape. Whereas at higher temperatures, most of them exhibit rod-like feature. The nanoparticle products have been also characterized by field emission scanning electron microscopy and X-ray diffraction techniques.

Π-conjugated porous polymers with hierarchical pore structures were synthesized via high internal phase emulsion polymerization (polyHIPE) technique. The polymers could be used as heterogeneous photocatalysts for highly selective oxidation of organic sulfides into sulfoxides and the free radical polymerization of methyl methacrylate (MMA) under visible light irradiation.

The superstructures of different morphology (superlattices and supercrystals) are obtained by self-organization of lead sulfide quantum dots (QDs) on a substrate. In contrast to the SAXS patterns of isolated QDs in solutions, the X-ray intensity from ordered superstructures is modulated by the interference from the QDs in SLs or SCs leading to occurrence of the intense peaks at small scattering angles. By indexing the peaks in the SAXS patterns it is concluded that QD SLs are close-packed QD ensembles with the lattice parameter close to the dot diameter and QD SCs have primitive orthorhombic crystal lattice. Absorption and photoluminescence bands of superstructures are also analyzed.

Important to the development of dye-sensitized solar cells is the longevity and photo-conversion efficiency of the dye. To improve cost effectiveness, dyes of superior thermal and chemical stability are desirable to extend device performance. In this study, we examine a series of peripherally fluorinated Zinc-Phthalocyanines (FxZnPc). Introduction of chemically inert fluorine and isopropyl fluoroalkyl groups on the periphery of the Pc improve the dye stability and allow for tunable photo-physical properties. Additionally, introduction of the bulky isopropyl fluoroalkyl groups help mitigate molecular aggregation in thin films which is known to be detrimental to maintaining the desired photo-physical properties of the surface coating. Using molecular dynamics and first principles modeling, various substituent effects on surface adhesion and aggregation over TiO2 surfaces are characterized for both symmetric and asymmetric substitution.