The impact of a TiO2/r-GO composite material on the performance of electron transport electrodes of dye sensitized solar cells.

In dye sensitized solar cells, the role of the electron transport layer is crucial because it makes it easier for photo-generated electrons to get from the dye to the external circuit. In DSSCs, the utilization of TiO2 is likely to be given preference in the production of electron transport electrodes due to its notable characteristics such as its expansive surface area, porosity, and capacity to scatter light. Nevertheless, the presence of heterogeneity within the mesoporous structure increases the likelihood of TiO2 aggregation, which subsequently diminishes the beneficial impact of TiO2 on the performance of DSSCs. In this context, reduced graphene oxide (r-GO) is introduced as an additive into the TiO2 network during the preparation of TiO2/reduced graphene oxide (r-GO) composites. The integration of r-GO with TiO2 has been recognized as a promising approach to enhance electron transport and electron lifespan, owing to remarkable qualities exhibited by r-GO. The present investigation involved the synthesis of a composite material including titanium dioxide/reduced graphene oxide (TiO2/r-GO) through the utilization of the co-precipitation technique. Following this, the generated TiO2/r-GO composite material and pure TiO2 were deposited on FTO through electrophoretic deposition to obtain an electron transport electrode of a dye sensitized solar cell. It should be noted that when r-GO was combined with TiO2, the performance of DSSCs improved notably compared to pure TiO2. As a result, the findings of this work have significant implications for the advancement of the TiO2/r-GO composite deposited through electrophoretic deposition. The power conversion efficiency reached 6.64% with the addition of r-GO in the metal oxide electron transport electrode. The obtained findings align with the outcomes of electrochemical impedance investigations in which the electrode constructed with TiO2/r-GO exhibits reduced electron transport resistance (RCt) at the anode/dye/electrolyte interface, as well as lower overall resistance (Rtotal) in comparison to TiO2-based DSSCs. These advancements have the potential to be employed in commercial DSSC manufacturing.

Electrochemical and power conversion performance of different counter electrode materials for flexible dye-sensitized solar cells.

Carbon dots and copper indium sulfide are promising photovoltaic materials, which have so far been fabricated mainly by chemical deposition methods. In this work, carbon dots (CDs) and copper indium sulfide (CIS) were separately combined with poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) for the preparation of stable dispersions. These prepared dispersions were used to produce CIS-PEDOT:PSS and CDs-PEDOT:PSS films using the ultrasonic spray deposition (USD) approach; furthermore, platinum (Pt) electrodes were fabricated and tested for flexible dye sensitized solar cells (FDSSCs). All the fabricated electrodes were utilized as counter electrodes for FDSSCs, and the power conversion efficiency of the FDSSCs reached 4.84% after 100 mW cm-2 AM1.5 white light was used to excite the cells. More investigation reveals that the improvement might be caused by the CDs film's porosity network and its strong connection to the substrate. These factors increase the number of sites available for the effective catalysis of redox couples in the electrolyte and facilitate the movement of charge in the FDSSC. It was also emphasized that the CIS film in the FDSSC device helps to generate a photo-current. In the beginning, this work shows how the USD approach can create CIS-PEDOT:PSS and CDs-PEDOT:PSS films and confirms that a CD based counter electrode film produced using the USD method is an interesting replacement for the Pt CE in FDSSC devices, while the results obtained from CIS-PEDOT:PSS are also comparable with standard Pt CE in FDSSCs.

Fabrication of cellulose paper-based counter electrodes for flexible dye-sensitized solar cells.

Here, we introduce the synthesis and deposition of organic/inorganic composite ink on cellulose paper using a rapid ultrasonic spray deposition approach that can be incorporated as a counter electrode (CE) in flexible dye-sensitized solar cells (FDSSCs). The composite ink comprised a copper indium sulfide (CuInS2) nanostructure ink and dispersion of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) in water. Fabricated counter electrodes are biodegradable, environment-friendly, flexible, and economical and meet the requirements for sustainable green energy. To evaluate the catalytic activities and power conversion efficiencies of DSSCs, the produced CuInS2/PEDOT:PSS composite ink-based CEs were compared with PEDOT:PSS counter electrodes. Cyclic voltammetry studies found that CuInS2/PEDOT:PSS had a greater cathodic charge transfer current density (Jc) (-1.23 mA cm-2). Moreover, it was found that the potential separation values are small, which indicate a stronger catalytic activity than PEDOT:PSS counter electrodes. The observed exchange current density (J0) was 3.98 mA cm-2, while the limiting current density (Jlim) increased to 45.7 mA cm-2, indicating a fast redox diffusion rate of the CuInS2/PEDOT:PSS CE. The photovoltaic performances of CuInS2/PEDOT:PSS and PEDOT: PSS-based DSSC's were measured and determined to be 5.66% and 4.41%, respectively, while the performance of CuInS2/PEDOT:PSS FDSSC composed of cellulose paper was 1.06%.

Green Synthesis of NiO-SnO2 Nanocomposite and Effect of Calcination Temperature on Its Physicochemical Properties: Impact on the Photocatalytic Degradation of Methyl Orange.

Background: Nickel stannate nanocomposites could be useful for removing organic and toxic water pollutants, such as methyl orange (MO). Aim: The synthesis of a nickel oxide-tin oxide nanocomposite (NiO-SnO2 NC) via a facile and economically viable approach using a leaf extract from Ficus elastica for the photocatalytic degradation of MO. Methods: The phase composition, crystallinity, and purity were examined by X-ray diffraction (XRD). The particles' morphology was studied using scanning electron microscopy (SEM). The elemental analysis and colored mapping were carried out via energy dispersive X-ray (EDX). The functional groups were identified by Fourier transform infrared spectroscopy (FTIR). UV-visible diffuse reflectance spectroscopy (UV-vis DRS) was used to study the optical properties such as the absorption edges and energy band gap, an important feature of semiconductors to determine photocatalytic applications. The photocatalytic activity of the NiO-SnO2 NC was evaluated by monitoring the degradation of MO in aqueous solution under irradiation with full light spectrum. The effects of calcination temperature, pH, initial MO concentration, and catalyst dose were all assessed to understand and optimize the physicochemical and photocatalytic properties of NiO-SnO2 NC. Results: NiO-SnO2 NC was successfully synthesized via a biological route using F. elastica leaf extract. XRD showed rhombohedral NiO and tetragonal SnO2 nanostructures and the amorphous nature of NiO-SnO2 NC. Its degree of crystallinity, crystallite size, and stability increased with increased calcination temperature. SEM depicted significant morphological changes with elevating calcination temperatures, which are attributed to the phase conversion from amorphous to crystalline. The elemental analysis and colored mapping show the formation of highly pure NiO-SnO2 NC. FTIR revealed a decrease in OH, and the ratio of oxygen vacancies at the surface of the NC can be explained by a loss of its hydrophilicity at increased temperatures. All the NC samples displayed significant absorption in the visible region, and a blue shift is seen and the energy band gap decreases when increasing the calcination temperatures due to the dehydration and formation of compacted large particles. NiO-SnO2 NC degrades MO, and the photocatalytic performance decreased with increasing calcination temperature due to an increase in the crystallite size of the NC. The optimal conditions for the efficient NC-mediated photocatalysis of MO are 100 °C, 20 mg catalyst, 50 ppm MO, and pH 6. Conclusions: The auspicious performance of the NiO-SnO2 NCs may open a new avenue for the development of semiconducting p-n heterojunction catalysts as promising structures for removing undesirable organic pollutants from the environment.

Investigations into the Antifungal, Photocatalytic, and Physicochemical Properties of Sol-Gel-Produced Tin Dioxide Nanoparticles.

Transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), energy dispersive X-ray (EDX), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), and Fourier transform infrared (FTIR) spectroscopy were applied to evaluate the tin dioxide nanoparticles (SnO2 NPs) amalgamated by the sol-gel process. XRD was used to examine the tetragonal-shaped crystallite with an average size of 26.95 (±1) nm, whereas the average particle size estimated from the TEM micrograph is 20.59 (±2) nm. A dose-dependent antifun3al activity was performed against two fungal species, and the activity was observed to be increased with an increase in the concentration of SnO2 NPs. The photocatalytic activity of SnO2 NPs in aqueous media was tested using Rhodamine 6G (Rh-6G) under solar light illumination. The Rh-6G was degraded at a rate of 0.96 × 10-2 min for a total of 94.18 percent in 350 min.

The Development of Highly Fluorescent Hemicyanine and Dicyanoisophorone Dyes for Applications in Dye-Sensitized Solar Cells.

Ruthenium-based metal complex dyes have been employed extensively in dye-sensitized solar cells (DSSCs) as photosensitizers, but the cost and toxicity of metal complexes have promoted the development of metal-free organic dyes. The present investigation deals with the synthesis of hemicyanine and Dicyanoisophorone (DCI) based dyes adopting the D-π-A strategy, and their application on sensitization of nano-crystalline ZnO electrodes by appending the carboxyl (COOH) anchoring group as a pendant on the primary skeleton of dyes. Dyes have been characterized by UV, FTIR, and NMR spectroscopic studies. Absorption maxima (λmax) were found in the region 416-551 nm while emission wavelength (λem) was observed in the range 575-685 nm. Cyclic voltammetry and DFT calculations were used to estimate redox potential and band gap energies of dyes.

Optical Absorption Cross Section of Individual Multi-Walled Carbon Nanotubes in the Visible Region.

The aim of the present work is to determine the optical absorption cross section for visible radiation of various types of multiwall carbon nanotubes (MWCNTs) having different dimensions through macroscopic optical measurements. This is achieved by dispersing MWCNTs in polydimethylsiloxane (PDMS) and preparing composite films. Different percentages (0.0% to 1.5%) of each MWCNTs type were mixed into the PDMS matrix using high speed mechanical stirring (~1000 rpm) and ultrasonication (~37 kHz) to reach optimal dispersion. By using doctor blading technique, 100 µm thick uniform films were produced on glass. They were then thermally cured and detached from the glass to get flexible and self-standing films. Field-Emission Scanning Electron Microscope (FESEM) analysis of cryo-fractured composite samples was used to check the dispersion of MWCNTs in PDMS, while Raman spectroscopy and FTIR were employed to rule out possible structural changes of the polymer in the composite that would have altered its optical properties. Total and specular reflection and transmission spectra were measured for all films. The absorption coefficient, which represents the fractional absorption per unit length and is proportional to the concentration of absorbing sites (i.e., MWCNTs at photon energies upon which PDMS is non-absorbing), was extracted. For each MWCNTs type, the absorption cross section of an individual MWCNT was obtained from the slope of absorption coefficient versus MWCNTs number density curve. It was found to be related with MWCNT volume. This method can be applied to all other nanoparticles as far as they can be dispersed in a host transparent matrix.

In-Situ Spectroscopic Analyses of the Dye Uptake on ZnO and TiO2 Photoanodes for Dye-Sensitized Solar Cells.

UV-Vis spectroscopic measurements have been performed on Dye-Sensitized Solar Cell (DSSC) photoanodes at different dye impregnation times ranging from few minutes to 24 hours. In addition to the traditional absorbance experiments, based on diffuse and specular reflectance of dye impregnated thin films and on the desorption of dye molecules from the photoanodes by means of a basic solution, an alternative in-situ solution depletion measurement, which enables fast and continuous evaluation of dye uptake, has been employed. Two different nanostructured semiconducting oxide films (mesoporous TiO2 and sponge-like ZnO) and two different dyes, the traditional Ruthenizer 535-bisTBA (N719) and a newly introduced metal-free organic dye based on a hemi-squaraine molecule (CT1), have been analyzed. DSSCs have been fabricated with the dye-impregnated photoanodes using a customized microfluidic architecture. The dye adsorption results are discussed and correlated to the obtained DSSC electrical performances such as photovoltaic conversion efficiencies and Incident Photon-to-electron Conversion Efficiency (IPCE) spectra. It is shown that simple UV-Vis measurements can give useful insights on the dye adsorption mechanisms and on the evaluation of the optimal impregnation times.

Ultrafast room-temperature crystallization of TiO2 nanotubes exploiting water-vapor treatment.

In this manuscript a near-room temperature crystallization process of anodic nanotubes from amorphous TiO2 to anatase phase with a fast 30 minutes treatment is reported for the first time. This method involves the exposure of as-grown TiO2 nanotubes to water vapor flow in ambient atmosphere. The water vapor-crystallized samples are deeply investigated in order to gain a whole understanding of their structural, physical and chemical properties. The photocatalytic activity of the converted material is tested by dye degradation experiment and the obtained performance confirms the highly promising properties of this low-temperature processed material.

Combined experimental and theoretical investigation of the hemi-squaraine/TiO2 interface for dye sensitized solar cells.

A simple hemi-squaraine dye (CT1) has been studied as a TiO2 sensitizer for application in dye sensitized solar cells (DSCs) by means of a combined experimental and theoretical investigation. This molecule is a prototype dye presenting an innovative anchoring group: the squaric acid moiety. Ab initio calculations based on Density Functional Theory (DFT) predict that this acid spontaneously deprotonates at the anatase (101) surface forming chemical bonds that are stronger than the ones formed by other linkers (e.g. cathecol and isonicotinic acid). Moreover an analysis of the electronic structure of the hybrid interface reveals the formation of a type II heterostructure ensuring adiabatic electron transfer from the molecule to the oxide. DSCs containing hemi-squaraine dyes were assembled, characterized and their performances compared to state of the art cells. Experimental results (large incident photon-to-electron conversion efficiency and an efficiency of 3.54%) confirmed the theoretical prediction that even a simple hemi-squaraine is an effective sensitizer for TiO2. Our study paves the way to the design of more efficient sensitizers based on a squaric acid linker and specifically engineered to absorb light in a larger part of the visible range.

High efficiency dye-sensitized solar cells exploiting sponge-like ZnO nanostructures.

Sponge-like nanostructured ZnO layers were successfully employed as photoanodes for the fabrication of highly efficient dye-sensitized solar cells. The sponge-like ZnO layers were obtained by room temperature radio-frequency magnetron sputtering deposition of metallic zinc, followed by thermal oxidation treatment in an ambient atmosphere. The porous films show a 3D branched nanomorphology, with a feature similar to natural coral. The morphological and optical properties of these layers were studied through field emission scanning electron microscopy, specific surface area measurements, ultraviolet-visible transmittance and absorption spectroscopy. The sponge-like ZnO film presents a high density of branches, with a relatively high specific surface area value, and fine optical transmittance. The morphology of the porous structure provides a high number of adsorption sites for the anchoring of sensitizer molecules, making it suitable for the fabrication of ZnO-based photoanodes for dye-sensitized solar cells. The light harvesting performance of the sensitized semiconductor was evaluated by current density vs. voltage measurements, incident photon-to-electron conversion efficiency, open circuit voltage decay and impedance spectroscopy. The modelling of the electrical characteristics evidences a higher electron lifetime and a longer charge diffusion length, if compared to standard TiO(2) nanoparticle based photoanodes. For ZnO films with a thickness up to 18 µm, a photoconversion efficiency as high as 6.67% and a maximum value of the incident photon-to-electron collection efficiency equal to 87% at 530 nm were demonstrated.