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1. New insights into the deterioration of TiO2 based oil paints: the effects of illumination conditions and surface interactions

   https://doi.org/10.1186/s40494-022-00733-2  

   Schmitt, Thomas ; Rosi, Francesca ; Mosconi, Edoardo ; Shull, Ken ; Fantacci, Simona ; Miliani, Costanza ; Gray, Kimberly ( June 2022 , Heritage Science)

   Titanium dioxide (TiO₂) has been used in numerous paintings since its creation in the early 1920s. However, due to this relatively recent adoption by the art world, we have limited knowledge about the nature and risk of degradation in museum environments. This study expands on the existing understanding of TiO₂facilitated degradation of linseed oil, by examining the effect of visible light and crystallographic phase (either anatase or rutile) on the reactivity of TiO₂. The present approach is based on a combination of experimental chemical characterization with computational calculation through Density Functional Theory (DFT) modeling of the TiO₂-oil system. Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FT-IR) enabled the identification of characteristic degradation products during UV and visible light aging of both rutile and anatase based paints in comparison to BaSO₄and linseed oil controls. In addition, cratering and cracking of the paint surface in TiO₂based paints, aged under visible and UV–vis illumination, were observed through Scanning Electron Microscopy (SEM). Finally, Density Functional Theory (DFT) modeling of interactions between anatase TiO₂and oleic acid, a fatty acid component of linseed oil, to form a charge transfer complex explains one possible mechanism for the visible light activity observed in artificial aging. Visible lightmore »excitation of this complex sensitizes TiO₂by injecting an electron into the conduction band of TiO₂to generate reactive oxygen species and subsequent degradation of the oil binder by various mechanisms (e.g., formation of an oleic acid cation radical and other oxidation products).

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2. Electron Transfer in Rhodamine–TiO2 Complexes Studied as a Function of Chalcogen and Bridge Substitution

   https://doi.org/10.1021/acs.jpcc.9b11049  

   Zachary Piontkowski, Yu-Chen Wang ( January 2020 , The journal of physical chemistry)

   Many emerging light-harvesting systems for solar-energy capture depend on absorption of light by molecular dyes and subsequent electron transfer to metal-oxide semiconductors. However, the inhomoge- neous electron-transfer process is often misunderstood when analogies from bimolecular electron transfer are used to explain experimental trends. Here, we develop and apply a theoretical methodology that correctly incorporates the semiconductor density of states and the system reorganization energies to explain observed trends in a series of molecular sensitizers. The effects of chalcogen and bridge substitution on the electron transfer in rhodamine− TiO2 complexes are theoretically investigated by combining density functional theory (DFT)/time-dependent DFT calculations and Fermi’s golden rule for the rate constant. It is shown that all dyes exhibit τeT < 4 ps. Dyes with thiophene bridges exhibit shorter τeT (∼1 ps) than dyes with phenylene bridges (∼4 ps). When the planes of the dye core and bridge are fixed at coplanarity, the dye−TiO2 coupling strength is found to increase by a factor of ∼2 when compared with the Franck− Condon geometry. However, the donor energy level of coplanar dyes falls significantly below the TiO2 conduction band edge so that, despite enhanced coupling, electron transfer is slowed to ∼20 ps. Similar results appear formore »the excited triplet states of these dyes, showing that the intersystem crossing to low energy triplet states can increase electron-transfer time constants to 60−240 ps. These results are compared to the results of previous photocatalytic hydrogen generation and dye-sensitized solar cell experiments.« less
3. Cascade synthesis and optoelectronic applications of intermediate bandgap Cu3VSe4 nanosheets

   https://doi.org/10.1038/s41598-020-78649-9  

   Liu, Mimi ; Lai, Cheng-Yu ; Zhang, Meng ; Radu, Daniela R. ( December 2020 , Scientific Reports)

   Two-dimensional (2D) ternary materials recently generated interest in optoelectronics and energy-related applications, alongside their binary counterparts. To date, only a few naturally occurring layered 2D ternary materials have been explored. The plethora of benefits owed to reduced dimensionality prompted exploration of expanding non-layered ternary chalcogenides into the 2D realm. This work presents a templating method that uses 2D transition metal dichalcogenides as initiators to be converted into the corresponding ternary chalcogenide upon addition of copper, via a solution-phase synthesis, conducted in high boiling point solvents. The process starts with preparation of VSe₂nanosheets, which are next converted into Cu₃VSe₄sulvanite nanosheets (NSs) which retain the 2D geometry while presenting an X-ray diffraction pattern identical with the one for the bulk Cu₃VSe₄. Both the scanning electron microscopy and transmission microscopy electron microscopy show the presence of quasi-2D morphology. Recent studies of the sulfur-containing sulvanite Cu₃VS₄highlight the presence of an intermediate bandgap, associated with enhanced photovoltaic (PV) performance. The Cu₃VSe₄nanosheets reported herein exhibit multiple UV–Vis absorption peaks, related to the intermediate bandgaps similar to Cu₃VS₄and Cu₃VSe₄nanocrystals. To test the potential of Cu₃VSe₄NSs as an absorber for solar photovoltaic devices, Cu₃VSe₄NSs thin-films deposited on FTO were subjected to photoelectrochemical testing, showing p-type behavior andmore »stable photocurrents of up to ~ 0.036 mA/cm². The photocurrent shows a ninefold increase in comparison to reported performance of Cu₃VSe₄nanocrystals. This proves that quasi-2D sulvanite nanosheets are amenable to thin-film deposition and could show superior PV performance in comparison to nanocrystal thin-films. The obtained electrical impedance spectroscopy signal of the Cu₃VSe₄ NSs-FTO based electrochemical cell fits an equivalent circuit with the circuit elements of solution resistance (R_s), charge-transfer resistance (R_ct), double-layer capacitance (C_dl), and Warburg impedance (W). The estimated charge transfer resistance value of 300 Ω cm²obtained from the Nyquist plot provides an insight into the rate of charge transfer on the electrode/electrolyte interface.

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4. Open-shell donor–π–acceptor conjugated metal-free dyes for dye-sensitized solar cells

   https://doi.org/10.1039/D0ME00091D  

   Sabuj, Md Abdus ; Rai, Neeraj ( November 2020 , Molecular Systems Design & Engineering)

   Dye-sensitized solar cells (DSCs) have drawn a significant interest due to their low production cost, design flexibility, and the tunability of the sensitizer. However, the power conversion efficiency (PCE) of the metal-free organic dyes is limited due to the inability of the dye to absorb light in the near-infrared (NIR) region, leaving a large amount of energy unused. Herein, we have designed new DSC dyes with open-shell character, which significantly red-shifts the absorption spectra from their counterpart closed-shell structure. A small diradical character ( y < 0.10) is found to be beneficial in red-shifting the absorption maxima into the NIR region and broadening up to 2500 nm. Also, the open-shell dyes significantly reduce the singlet–triplet energy gaps (Δ E ST ), increase the total amount of charge-transfer to the semiconductor surface, reduce the exciton binding energy, and significantly increase the excited-state lifetimes compared to the closed-shell systems. However, the closed-shell dyes have higher injection efficiency with increased intramolecular charge transfer (ICT) character. Our study reveals the design rule for open-shell DSC dyes to be able to absorb photons in the NIR region, which can increase the efficiency of the solar cell device.
5. An Open Source, Iterative Dual-Tree Wavelet Background Subtraction Method Extended from Automated Diffraction Pattern Analysis to Optical Spectroscopy

   https://doi.org/10.1177/0003702819871330  

   Chevalier, Robert B. ; Dwyer, Jason R. ( December 2019 , Applied Spectroscopy)

   Background subtraction is a general problem in spectroscopy often addressed with application-specific techniques, or methods that introduce a variety of implementation barriers such as having to specify peak-free regions of the spectrum. An iterative dual-tree complex wavelet transform-based background subtraction method (DTCWT-IA) was recently developed for the analysis of ultrafast electron diffraction patterns. The method was designed to require minimal user intervention, to support streamlined analysis of many diffraction patterns with complex overlapping peaks and time-varying backgrounds, and is implemented in an open-source computer program. We examined the performance of DTCWT-IA for the analysis of spectra acquired by a range of optical spectroscopies including ultraviolet–visible spectroscopy (UV–Vis), X-ray photoelectron spectroscopy (XPS), and surface-enhanced Raman spectroscopy (SERS). A key benefit of the method is that the user need not specify regions of the spectrum where no peaks are expected to occur. SER spectra were used to investigate the robustness of DTCWT-IA to signal-to-noise levels in the spectrum and to user operation, specifically to two of the algorithm parameter settings: decomposition level and iteration number. The single, general DTCWT-IA implementation performs well in comparison to the different conventional approaches to background subtraction for UV–Vis, XPS, and SERS, while requiring minimal input. Themore »method thus holds the same potential for optical spectroscopy as for ultrafast electron diffraction, namely streamlined analysis of spectra with complex distributions of peaks and varying signal levels, thus supporting real-time spectral analysis or the analysis of data acquired from different sources.« less