Size-Controlled Cu3VSe4 Nanocrystals as Cathode Material in Platinum-Free Dye-Sensitized Solar Cells.

In this work, we report the first single-step, size-controlled synthesis of Cu3VSe4 cuboidal nanocrystals, with the longest dimension ranging from 9 to 36 nm, and their use in replacing the platinum counter electrode in dye-sensitized solar cells. Cu3VSe4, a ternary semiconductor from the class of sulvanites, is theoretically predicted to have good hole mobility, making it a promising candidate for charge transport in solar photovoltaic devices. The identity and crystalline purity of the Cu3VSe4 nanocrystals were validated by X-ray powder diffraction (XRD) and Raman spectroscopy. The particle size was determined from the XRD data using the Williamson-Hall equation and was found in agreement with the transmission electron microscopy imaging. Based on the electrochemical activity of the Cu3VSe4 nanocrystals, studied by cyclic voltammetry, the nanomaterials were further employed for fabricating counter electrodes (CEs) in Pt-free dye-sensitized solar cells. The counter electrodes were prepared from Cu3VSe4 nanocrystals as thin films, and the charge transfer kinetics were studied by electrochemical impedance spectroscopy. The work demonstrates that Cu3VSe4 counter electrodes successfully replace platinum in DSSCs. CEs fabricated with the Cu3VSe4 nanocrystals having an average particle size of 31.6 nm outperformed Pt, leading to DSSCs with the highest power conversion efficiency (5.93%) when compared with those fabricated with the Pt CE (5.85%).

Lignin-Based Nanospheres as Environmental Remediation Platforms for Anionic Dye Contaminants.

Modern manufacturing of textiles, pharmaceuticals, food, cosmetics, plastics, paper, etc. involves the utilization of anionic and cationic dyes that lead to significant water contamination. Recent research has explored the use of nanomaterials toward developing nanoadsorbents for water decontamination caused by industrial pollution. Here, we report on a novel platform for anionic dye remediation, consisting of a polyethylenimine-functionalized lignin nanosphere (PEI-LNS). The designed nanomaterial shows significant ability to adsorb an anionic dye selected as a proof-of-concept-Sulforhodamine B, from aqueous solutions. The PEI lignin nanoadsorbents (PEI-LNS) showed a better ability to adsorb Sulforhodamine B sodium salt (SBSS) when compared to the raw lignin nanosphere adsorbent (LNS), especially in acidic conditions. The nanomaterial was characterized through transmission electron microscopy, scanning electron microscopy, Brunauer-Emmett-Teller surface area analysis, elemental analysis, zeta potential, thermogravimetric analysis, Fourier transform infrared spectroscopy, and nuclear magnetic resonance. The impacts of ionic strength, contact time, pH, and adsorbent concentration have been evaluated. The ability of PEI-LNS to adsorb SBSS was found to be consistent with Langmuir isotherms and pseudo-second-order kinetic models. The PEI-LNS could be recycled three times, reaching a good (85%) adsorbing capacity even in the third cycle. The study demonstrates that PEI-LNS has a strong affinity as a novel adsorbent for anionic dyes and could be employed in environmental cleanups pertaining to such contaminations.

Universality and scaling in complex networks from periods of Chinese history.

Critical physical systems with large numbers of molecules can show universal and scaling behaviors. It is of interest to know whether human societies with large numbers of people can show the same behaviors. Here, we use network theory to analyze Chinese history in periods 209 BCE-23 CE and 515-618 CE) related to the Western Han-Xin Dynasty and the late Northern Wei-Sui Dynasty, respectively. Two persons are connected when they appear in the same historical event. We find that the historical networks from two periods separated about 500 years have interesting universal and scaling behaviors, and they are small-world networks; their average cluster coefficients as a function of degree are similar to the network of movie stars. In the historical networks, the persons with larger degrees prefer to connect with persons with a small degree; however, in the network of movie stars, the persons with larger degrees prefer to connect with persons with large degrees. We also find an interesting similar mechanism for the decline or collapse of historical Chinese dynasties. The collapses of the Xin dynasty (9-23 CE) and the Sui dynasty (581-618 CE) were initiated from their arrogant attitude toward neighboring states.

Infrared-Activated Bactericide: Rhenium Disulfide (ReS2)-Functionalized Mesoporous Silica Nanoparticles.

An attractive strategy for treating bacterial infection is the combination of antibiotic chemotherapy with photothermal therapy (PTT), which could be implemented using multifunctional nanomaterials. In this work, the intrinsic photothermal efficiency of two-dimensional (2D) rhenium disulfide (ReS2) nanosheets is enhanced by their coating on mesoporous silica nanoparticles (MSNs) to realize a highly efficient light-responsive nanoparticle endowed with controlled-release drug delivery capability, denoted as MSN-ReS2. The MSN component of the hybrid nanoparticle features augmented pore size toward facilitating increased loading of antibacterial drugs. The ReS2 synthesis is conducted in the presence of MSNs through an in situ hydrothermal reaction and leads to a uniform surface coating of the nanosphere. The MSN-ReS2 bactericide testing showed more than 99% bacterial killing efficiency in both Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus) upon laser irradiation. A cooperative effect that led to a 100% bactericide effect on Gram-negative bacteria (E. coli) was observed when tetracycline hydrochloride was loaded in the carrier. The results show the potential of MSN-ReS2 to be used as a wound-healing therapeutic with a synergistic bactericide role.

Colloidal Synthesis and Photocatalytic Properties of Cu3NbS4 and Cu3NbSe4 Sulvanite Nanocrystals.

Niobium sulvanites Cu3NbX4 (X = S, Se) have been theoretically predicted as promising candidates for solar photovoltaics and photocatalytic water splitting. This report outlines the first synthesis of Cu3NbS4 and Cu3NbSe4 in a nanocrystalline form. The crystal structures were investigated by X-ray diffraction, identity was confirmed by Raman spectroscopy, and the optoelectronic properties and morphology of Cu3NbS4 and Cu3NbSe4 nanocrystals were examined by UV-vis spectroscopy and transmission electron microscopy, respectively. To gain insight into the Cu3NbX4 formation, a mechanistic study was conducted for Cu3NbSe4 monitoring the nanoparticles' formation as a function of reaction time. Methylene blue photodegradation tests were conducted to evaluate the photoactivity of Cu3NbS4 and Cu3NbSe4. The degradation rates, 2.81 × 10-2 min-1 and 1.22 × 10-2 min-1 proved the photocatalysts' potential of nanoscale Cu3NbX4.

Photocatalytic Deposition of Nanostructured CsPbBr3 Perovskite Quantum Dot Films on Mesoporous TiO2 and Their Enhanced Visible-Light Photodegradation Properties.

Herein, we report the in situ photocatalytic deposition of cesium lead bromide (CsPbBr3) perovskite quantum dots on mesoporous TiO2-coated fluorine-doped tin oxide (FTO/TiO2) electrodes. The mesoporous TiO2 layer is used as a photocatalyst to promote the following: (1) the Pb deposition from a Pb2+ aqueous solution and (2) the in situ Pb conversion into CsPbBr3 perovskite in the presence of a CsBr methanolic solution without any organic capping agent. Both steps are carried out under ultraviolet light irradiation under ambient conditions without any post-treatment. The obtained FTO/TiO2/CsPbBr3 film was characterized by UV-vis diffuse reflectance spectroscopy, X-ray diffraction, photoluminescence spectroscopy, scanning electron microscopy, and transmission electron microscopy. The FTO/TiO2/CsPbBr3 heterojunction exhibited enhanced visible-light photodegradation activity demonstrated for the oxidation of curcumin organic dye as a model system. The novel and simple approach to fabricating a supported photocatalyst represents a scalable general method to use semiconductors as a platform to incorporate different perovskites, either all-inorganic or hybrid, for optoelectronic applications. The perovskite deposition method mediated by the UV light at room temperature could be further applied to flexible and wearable solar power electronics.

Sulvanites: The Promise at the Nanoscale.

The class of ternary copper chalcogenides Cu3MX4 (M = V, Nb, Ta; X = S, Se, Te), also known as the sulvanite family, has attracted attention in the past decade as featuring promising materials for optoelectronic devices, including solar photovoltaics. Experimental and theoretical studies of these semiconductors have provided much insight into their properties, both in bulk and at the nanoscale. The recent realization of sulvanites at the nanoscale opens new avenues for the compounds toward printable electronics. This review is aimed at the consideration of synthesis methods, relevant properties and the recent developments of the most important sulvanites.

Femtosecond time-evolution of mid-infrared spectral line shapes of Dirac fermions in topological insulators.

Mid-infrared (MIR) light sources have much potential in the study of Dirac-fermions (DFs) in graphene and topological insulators (TIs) because they have a low photon energy. However, the topological surface state transitions (SSTs) in Dirac cones are veiled by the free carrier absorption (FCA) with same spectral line shape that is always seen in static MIR spectra. Therefore, it is difficult to distinguish the SST from the FCA, especially in TIs. Here, we disclose the abnormal MIR spectrum feature of transient reflectivity changes (ΔR/R) for the non-equilibrium states in TIs, and further distinguish FCA and spin-momentum locked SST using time-resolved and linearly polarized ultra-broadband MIR spectroscopy with no environmental perturbation. Although both effects produce similar features in the reflection spectra, they produce completely different variations in the ΔR/R to show their intrinsic ultrafast dynamics.

A curvature-tunable random laser.

The application of random lasers has been restricted due to the absence of a well-defined resonant cavity, as the lasing action mainly depends on multiple light scattering induced by intrinsic disorders of the laser medium to establish the required optical feedback that hence increases the difficulty in efficiently tuning and modulating random lasing emissions. This study investigated whether the transport mean free path of emitted photons within disordered scatterers composed of ZnO nanowires is tunable by a curvature bending applied to the flexible polyethylene terephthalate (PET) substrate underneath, thereby creating a unique light source that can be operated above and below the lasing threshold for desirable spectral emissions. For the first time, the developed curvature-tunable random laser is implemented for in vivo biological imaging with much lower speckle noise compared to the non-lasing situation through simple mechanical bending, which is of great potential for studying the fast-moving physiological phenomenon such as blood flow patterns in mouse ear skin. It is expected that the experimental demonstration of the curvature-tunable random laser can provide a new route to develop disorder-based optoelectronic devices.

Optimal degradation of dye wastewater by ultrasound/Fenton method in the presence of nanoscale iron.

An advanced ultrasound/Fenton/nanoscale iron oxidation process was applied for treatment of dye wastewater. In this study, the Taguchi statistical method was used to design experiments for the optimization of the ultrasound/Fenton/nanoscale iron process. The experimental design consisted of testing five factors (dosage of H(2)O(2), concentration of Fe(2 + ), amount of nanoscale iron added, treatment time, and initial pH), with four levels of each factor tested. Chemical oxygen demand (COD) measurements were conducted to determine the efficiency of the water samples. An analysis of the mean sign-to-noise (S/N) ratio indicated that the optimum combination of levels of the factors providing maximal COD reduction of aqueous azo dyes (500 mg/L) were: treatment time = 60 min, dosage of nanoscale iron = 1 g/L, initial pH = 2, and ratio of [dye]:[H(2)O(2)]:[Fe(2 + )]=1:3.6:2.4. The efficiencies of decolorization and COD reduction were accomplished under these optimum conditions at levels of 99.91% and 63.36%, respectively. The percentage contribution of each factor was determined by the analysis of variance (ANOVA). The results show that the contributions of the five factors-dosage of H(2)O(2), concentration of Fe(2 + ), amount of nanoscale iron added, treatment time, and initial pH-were 29.33%, 21.37%, 22.51%, 12.93% and 12.35%, respectively.

Establishment of activity indicator of TiO2 photocatalytic reaction--hydroxyl radical trapping method.

In this study, a new, low cost and easy method, hydroxyl radical trapping method, was employed to investigate the photo-activity of UV/TiO2 photocatalytic reaction. The Taguchi method was utilized to optimize the preparation of titanium dioxide (TiO2) thin-film reactor through the modified chemical vapor deposition (CVD) method. The optimal yield of hydroxyl radicals was then evaluated by calculating the conversion ratio of salicylic acid under the optimal conditions. In the experiments, salicylic acid was used as the free-radical scavenger and the formation of three different intermediates were examined to shed light on the trend and kinetics of reaction of hydroxyl radical with organic substance under different operation conditions. The results indicated that the yield of hydroxyl radicals increased with increasing irradiation intensity and dissolved oxygen level. The optimal experimental conditions obtained in this study were irradiation with intensity of 2.9 mW cm(-2) on salicylic acid at concentration of 250 mg L(-1) by both agitation and aeration processes (dissolved oxygen level=8.2 mg O(2)L(-1)) at pH 5. Such conditions could achieve the optimal hydroxyl radical yield of 5.1 x 10(-17)M.

Effect of pH on Fenton process using estimation of hydroxyl radical with salicylic acid as trapping reagent.

This study estimates the yield of hydroxyl radical using salicylic acid as the trapping reagent and investigates the relationship between hydroxyl radical and pH value. The formation and variation of hydroxyl radical under different pH values were evaluated using reaction products, 2,3-DHBA, 2,5-DHBA, and catechol. The formation rate of hydroxyl radical was dependent on the ratio of ferrous ion to hydrogen peroxide and pH values. The difference between various pH values was explored. The kinetics and mechanisms of hydroxyl radical reactions were established in the Fenton process. Experimental results showed that the best reaction conditions were 8.5 mM H(2)O(2), 1.25 mM Fe(2 + ), Fe(2 + )/H(2)O(2) = 0.147 at pH 3 and the formation rate constant of hydroxyl radical was 1.12 x 10(11) M(-1) s(-1).

Characteristics of manganese-coated sand using SEM and EDAX analysis.

"Manganese-coated sand" is a type of silica medium coated with manganese oxides, formed from the sorption of manganese oxides during long-term filtration via the process of rapid sand filtration, followed by aeration in a water treatment plant. Locally available manganese-coated sand, both for packing and as a byproduct of filtration processes for water treatment plants in Taiwan, was found to be a low-cost and promising adsorbent for removal of Mn(2+) from raw water. This study was conducted to build the basic data for coating hydrated manganese oxide on the sand surface to utilize the adsorbent properties of the coating and the filtration properties of the sand. In this study, gas adsorption porosimetry and scanning electron microscopy analyses were used to investigate the surface properties of the coated layer. An energy dispersive X-ray (EDAX) technique of analysis was used to characterize metal adsorption sites on a manganese-coated sand surface. Results indicated that manganese-coated sand had more micropores and higher specific surface area, owing to attachment of manganese sand. Manganese ions penetrated into the micropores and mesopores of manganese oxide on a sandy surface; regeneration of manganese-coated sand could be achieved by soaking with pH < 2.0 acid solution. Results of EDAX analysis showed that the interfacial layer constructed the interface of manganese-coated sand. Acid and alkali resistance tests interpret a wide application range of pH for manganese-coated sand, and general temperature conditions do not affect the performance of this sand. Manganese-coated sand is potentially suitable for application as a packed bed for treatment of heavy metals from water. The results of this study can also benefit plant operational capacity data for engineering design.

The reaction pathway for the heterogeneous photocatalysis of trichloroethylene in gas phase.

Trichloroethylene (TCE) has been widely used in industry. It is considered a hazardous and carcinogenic air pollutant. In this investigation, TCE photocatalytic reactions were performed in a packed bed reactor configured as a continuous flow reactor and a FT-IR sample cell used as a batch reactor to determine the intermediates under irradiation by 365 nm UV light. In this study, the intermediates detected during these reactions were phosgene, dichloroacetyl chloride (DCAC), chloroform, hexachloroethane, alcohols, esters, aldehydes, carbon monoxide, and carbon dioxide. The possible reaction mechanisms began with the Cl- subtraction. The Cl radicals then interacted with TCE to form various intermediates and products.