Photocatalytic nanocomposite membranes for environmental remediation.

We report the design and one-pot synthesis of Ag-doped BiVO4embedded in reduced graphene oxide (BiVO4:Ag/rGO) nanocomposites via a hydrothermal processing route. The binary heterojunction photocatalysts exhibited high efficiency for visible light degradation of model dyes and were correspondingly used for the preparation of photocatalytic membranes using polyvinylidene fluoride (PVDF) or polyethylene glycol (PEG)-modified polyimide (PI), respectively. The surface and cross-section images combined with elemental mapping illustrated the effective distribution of the nanocomposites within the polymeric membranes. Photocatalytic degradation efficiencies of 61% and 70% were achieved after 5 h of visible light irradiation using BiVO4:Ag/rGO@PVDF and BiVO4:Ag/rGO@PI (PEG-modified) systems, respectively. The beneficial photocatalytic performance of the BiVO4:Ag/rGO@PI (PEG-modified) membrane is explained by the higher hydrophilicity due to the PEG modification of the PI membrane. This work may provide a rational and effective strategy to fabricate highly efficient photocatalytic nanocomposite membranes with well-contacted interfaces for environmental purification.

Self-cleaning, photocatalytic films on aluminum plates for multi-pollutant air remediation: promoting adhesion and activity by SiO2interlayers.

In recent years, nanoparticles have come under close scrutiny for their possible health and environmental issues, making them less attractive for photocatalytic applications in air or water purification. Replacing free nano-powders with active and stable films is thus a fundamental step towards developing effective photocatalytic devices. Aluminum represents a cheap and technologically-relevant substrate, but its photocatalytic applications have been hampered by adhesion issues and metal ion diffusion within the photocatalytic layer. In this work, the use of silica interlayers is investigated as a strategy to promote adhesion, efficiency and reusability of TiO2films deposited on aluminum plates. Films were prepared from stable titania sols to avoid the use of nano-powders. Aluminum substrates with different surface morphology were investigated and the role of the silica interlayer thickness was studied. Films were extensively characterized, studying their structure, morphology, optical properties, adhesion and hardness. Self-cleaning properties were studied with respect to their superhydrophilicity and ability to resist fouling via alkylsilanes. Photocatalytic degradation tests were carried out using both volatile organic compounds and NOx, also in recycle tests. The presence of the silica interlayer proved crucial to promote the film robustness and photocatalytic activity. The substrate morphology determined the optimal interlayer thickness, especially in terms of the film reusability.

Deposition of Hybrid Photocatalytic Layers for Air Purification Using Commercial TiO2 Powders.

Photocatalytic nanomaterials, using only light as the source of excitation, have been developed for the breakdown of volatile organic compounds (VOCs) in air for a long time. It is a tough challenge to immobilize these powder photocatalysts and prevent their entrainment with the gas stream. Conventional methods for making stable films typically require expensive deposition equipment and only allow the deposition of very thin layers with limited photocatalytic performance. The present work presents an alternative approach, using the combination of commercially available photocatalytic nanopowders and a polymer or inorganic sol-gel-based matrix. Analysis of the photocatalytic degradation of ethanol was studied for these layers on metallic substrates, proving a difference in photocatalytic activity for different types of stable layers. The sol-gel-based TiO2 layers showed an improved photocatalytic activity of the nanomaterials compared with the polymer TiO2 layers. In addition, the used preparation methods require only a limited amount of photocatalyst, little equipment, and allow easy upscaling.

Identification of Dy

Laser excitation and x-ray spectroscopy are combined to settle a long-standing question in persistent luminescence. A reversible electron transfer is demonstrated, controlled by light and showing the same kinetics as the persistent luminescence. Exposure to violet light induces charging by oxidation of the excited Eu^{2+} while Dy^{3+} is simultaneously reduced. Oppositely, detrapping of Dy^{2+} occurs at ambient temperature or by infrared illumination, yielding afterglow or optically stimulated luminescence, respectively.

Switchable Piezoresistive SmS Thin Films on Large Area.

Samarium monosulfide (SmS) is a switchable material, showing a pressure-induced semiconductor to metal transition. As such, it can be used in different applications such as piezoresistive sensors and memory devices. In this work, we present how e-beam sublimation of samarium metal in a reactive atmosphere can be used for the deposition of semiconducting SmS thin films on 150 mm diameter silicon wafers. The deposition parameters influencing the composition and properties of the thin films are evaluated, such as the deposition rate of Sm metal, the substrate temperature and the H2S partial pressure. We then present the changes in the optical, structural and electrical properties of this compound after the pressure-induced switching to the metallic state. The back-switching and stability of SmS thin films are studied as a function of temperature and atmosphere via in-situ X-ray diffraction. The thermally induced back switching initiates at 250 °C, while above 500 °C, Sm2O2S is formed. Lastly, we explore the possibility to determine the valence state of the samarium ions by means of X-ray photoelectron spectroscopy.

Exploring Lanthanide Doping in UiO-66: A Combined Experimental and Computational Study of the Electronic Structure.

Lanthanide-based metal-organic frameworks show very limited stabilities, which impedes their use in applications exploiting their extraordinary electronic properties, such as luminescence and photocatalysis. This study demonstrates a fast and easy microwave procedure to dope UiO-66, an exceptionally stable and tunable Zr-based metal-organic framework. The generally applicable synthesis methodology is used to incorporate different transition metal and lanthanide ions. Selected experiments on these newly synthesized materials allow us to construct an energy scheme of lanthanide energy levels with respect to the UiO-66 host. The model is confirmed via absolute intensity measurements and provides an intuitive way to understand charge transfer mechanisms in these doped UiO-66 materials. Density functional theory calculations on a subset of materials moreover improve our understanding of the electronic changes in doped UiO-66 and corroborate our empirical model.

Predicting the afterglow duration in persistent phosphors: a validated approach to derive trap depth distributions.

Persistent phosphors are increasingly investigated due to their potential applications in various fields, such as safety signage, dosimetry and in vivo imaging. These materials act as optical batteries that store and gradually release energy supplied during optical charging. As the energy is stored, or 'trapped', at specific defect sites in the host lattice, a clear understanding of the defects and trapping mechanisms in these materials is important for systematic improvement of their properties. Here, the thermoluminescence and afterglow properties of the near-infrared (NIR) emitting persistent phosphor LiGa5O8:Cr3+ (LGO:Cr) are studied. This phosphor is used as a model system for illustrating a more general approach to reliably derive trap depth distributions in persistent luminescent and storage materials. The combination of the Tstop-Tmax method with initial rise analysis is used to experimentally determine the presence of a broad distribution of trapping states. Computerized glow curve fitting is subsequently used to extract the relevant trapping parameters of the system in a rigorous, consistent manner, by fitting all the experimentally recorded data simultaneously. The resulting, single set of model parameters is able to describe all measured thermoluminescence and afterglow data and hence can be used to predict afterglow and storage properties of the phosphor under various conditions. The methods to analyze and describe the trap structure of the persistent phosphor LGO:Cr are straightforwardly applicable for other persistent and storage phosphors and result in a reliable determination of the relevant trapping parameters of a given material.

Metal Organic Frameworks Based Materials for Heterogeneous Photocatalysis.

The increase in environmental pollution due to the excessive use of fossil fuels has prompted the development of alternative and sustainable energy sources. As an abundant and sustainable energy, solar energy represents the most attractive and promising clean energy source for replacing fossil fuels. Metal organic frameworks (MOFs) are easily constructed and can be tailored towards favorable photocatalytic properties in pollution degradation, organic transformations, CO2 reduction and water splitting. In this review, we first summarize the different roles of MOF materials in the photoredox chemical systems. Then, the typical applications of MOF materials in heterogeneous photocatalysis are discussed in detail. Finally, the challenges and opportunities in this promising field are evaluated.

Charge transfer induced energy storage in CaZnOS:Mn - insight from experimental and computational spectroscopy.

CaZnOS:Mn2+ is a rare-earth-free luminescent compound with an orange broadband emission at 612 nm, featuring pressure sensing capabilities, often explained by defect levels where energy can be stored. Despite recent efforts from experimental and theoretical points of view, the underlying luminescence mechanisms in this phosphor still lack a profound understanding. By the evaluation of thermoluminescence as a function of the charging wavelength, we probe the defect levels allowing energy storage. Multiple trap depths and trapping routes are found, suggesting predominantly local trapping close to Mn2+ impurities. We demonstrate that this phosphor shows mechanoluminescence which is unexpectedly stable at high temperature (up to 200 °C), allowing pressure sensing in a wide temperature range. Next, we correlate the spectroscopic results with a theoretical study of the electronic structure and stability of the Mn defects in CaZnOS. DFT calculations at the PBE+U level indicate that Mn impurities are incorporated on the Zn site in a divalent charge state, which is confirmed by X-ray absorption spectroscopy (XAS). Ligand-to-metal charge transfer (LMCT) is predicted from the location of the Mn impurity levels, obtained from the calculated defect formation energies. This LMCT proves to be a very efficient pathway for energy storage. The excited state landscape of the Mn2+ 3d5 electron configuration is assessed through the spin-correlated crystal field and a good correspondence with the emission and excitation spectra is found. In conclusion, studying phosphors at both a single-particle level (i.e. via calculation of defect formation energies) and a many-particle level (i.e. by accurately localizing the excited states) is necessary to obtain a complete picture of luminescent defects, as demonstrated in the case of CaZnOS:Mn2+.

Fe(II) Spin Transition Materials Including an Amino-Ester 1,2,4-Triazole Derivative, Operating at, below, and above Room Temperature.

A new family of one-dimensional Fe(II) 1,2,4-triazole spin transition coordination polymers for which a modification of anion and crystallization solvent can tune the switching temperature over a wide range, including the room temperature region, is reported. This series of materials was prepared as powders after reaction of ethyl-4H-1,2,4-triazol-4-yl-acetate (αEtGlytrz) with an iron salt from a MeOH/H2O medium affording: [Fe(αEtGlytrz)3](ClO4)2 (1); [Fe(αEtGlytrz)3](ClO4)2·CH3OH (2); [Fe(αEtGlytrz)3](NO3)2·H2O (3); [Fe(αEtGlytrz)3](NO3)2 (4); [Fe(αEtGlytrz)3](BF4)2·0.5H2O (5); [Fe(αEtGlytrz)3](BF4)2 (6); and [Fe(αEtGlytrz)3](CF3SO3)2·2H2O (7). Their spin transition properties were investigated by (57)Fe Mossbauer spectroscopy, superconducting quantum interference device (SQUID) magnetometry, and differential scanning calorimetry (DSC). The temperature dependence of the high-spin molar fraction derived from (57)Fe Mössbauer spectroscopy in 1 reveals an abrupt single step transition between low-spin and high-spin states with a hysteresis loop of width 5 K (Tc(↑) = 296 K and Tc(↓) = 291 K). The properties drastically change with modification of anion and/or lattice solvent. The transition temperatures, deduced by SQUID magnetometry, shift to Tc(↑) = 273 K and Tc(↓) = 263 K for (2), Tc(↑) = 353 K and Tc(↓) = 333 K for (3), Tc(↑) = 338 K and Tc(↓) = 278 K for (4), T(↑) = 320 K and T(↓) = 305 K for (5), Tc(↑) = 106 K and Tc(↓) = 92 K for (6), and T(↑) = 325 K and T(↓) = 322 K for (7). Annealing experiments of 3 lead to a change of the morphology, texture, and magnetic properties of the sample. A dehydration/rehydration process associated with a spin state change was analyzed by a mean-field macroscopic master equation using a two-level Hamiltonian Ising-like model for 3. A new structural-property relationship was also identified for this series of materials [Fe(αEtGlytrz)3](anion)2·nSolvent based on Mössbauer and DSC measurements. The entropy gap associated with the spin transition and the volume of the inserted counteranion shows a linear trend, with decrease in entropy with increasing the size of the counteranion. The first materials of this substance class to display a complete spin transition in both spin states are also presented.

Energy level modeling of lanthanide materials: review and uncertainty analysis.

Energy level schemes are an essential tool for the description and interpretation of atomic spectra. During the last 40 years, several empirical methods and relationships were devised for constructing energy level schemes of lanthanide defects in wide band gap solids, culminating in the chemical shift model by Thiel and Dorenbos. This model allows us to calculate the electronic and optical properties of the considered materials. However, an unbiased assessment of the accuracy of the obtained values of the calculated parameters is still lacking to a large extent. In this paper, error margins for calculated electronic and optical properties are deduced. It is found that optical transitions can be predicted within an acceptable error margin, while the description of phenomena involving conduction band states is limited to qualitative interpretation due to the large error margins for physical observables such as thermal quenching temperature, corresponding to standard deviations in the range 0.3-0.5 eV for the relevant energy differences. As an example, the electronic structure of lanthanide doped calcium thiogallate (CaGa2S4) is determined, taking the experimental spectra of CaGa2S4:Ln(Q+) (Ln(Q+) = Ce(3+), Eu(2+), Tm(3+)) as input. Two different approaches to obtain the shape of the zig-zag curves connecting the 4f levels of the different lanthanides are explored and compared.

Energy transfer in Eu³âº doped scheelites: use as thermographic phosphor.

In this paper the luminescence of the scheelite-based CaGd2(1-x)Eu2x(WO4)4 solid solutions is investigated as a function of the Eu content and temperature. All phosphors show intense red luminescence due to the 5D0 - 7F2 transition in Eu³âº, along with other transitions from the 5D1 and 5D0 excited states. For high Eu³âº concentrations the intensity ratio of the emission originating from the 5D1 and 5D0 levels has a non-conventional temperature dependence, which could be explained by a phonon-assisted cross-relaxation process. It is demonstrated that this intensity ratio can be used as a measure of temperature with high spatial resolution, allowing the use of these scheelites as thermographic phosphor. The main disadvantage of many thermographic phosphors, a decreasing signal for increasing temperature, is absent.

Hydrophilic, bright CuInS2 quantum dots as Cd-free fluorescent labels in quantitative immunoassay.

We report on the synthesis of core-shell CuInS2/ZnS quantum dots (QDs) in organic solution, their encapsulation with a PEG-containing amphiphilic polymer, and the application of the resulting water-soluble QDs as fluorescent label in quantitative immunoassay. By optimizing the methods for core synthesis and shell growth, CuInS2/ZnS QDs were obtained with a quantum yield of 50% on average after hydrophilization. After conjugation with an aflatoxin B1-protein derivative, the obtained QDs were used as fluorescent labels in microplate immunoassay for the quantitative determination of the mycotoxin aflatoxin B1. QDs-based immunoassay showed higher sensitivity compared to enzyme-based immunoassay.

Optical properties of root canal irrigants in the 300-3,000-nm wavelength region.

In root canal therapy, irrigating solutions are essential to assist in debridement and disinfection. Their spread and action is often restricted by canal anatomy, requiring some form of activation. Lasers have been shown to be promising tools for this purpose (laser-activated irrigation (LAI)). For LAI to be effective, high absorption of radiation in the irrigant is essential. Although the absorption spectrum of water is well established, little is known about the optical properties of other irrigating solutions. Therefore, root canal irrigants (sodium hypochlorite (NaOCl), citric acid (CA), chlorhexidine (CHX), ethylenediaminetetraacetate (EDTA), water) were subjected to UV/Vis spectrophotometry in the 300-3,000-nm region using synthetic quartz cells with an optical path length of 1 mm. Transmission data were used to plot the transmission spectrum and calculate the absorption coefficient (α) of each irrigant. The transmission spectra of the tested solutions proved to follow the spectrum of pure water to a large extent. All tested solutions displayed absorption peaks around 1,450 nm (α ≈ 14 cm(-1)), 1,950 nm (α > 30 cm(-1)), and above 2,500 nm (α > 30 cm(-1)). NaOCl showed higher absorption than water in the UV region. Slightly higher absorption than water was noted for CHX (Corsodyl) around 513 nm and for CA between 1,600 and 1,800 nm and around 2,200 nm. The absorption in all tested solutions for wavelengths greater than 2,500 nm is very high, meaning a great potential for laser-activated irrigation. Other wavelengths eligible for LAI are located around 1,450 and 2,000 nm but require further investigation.

Ratiometric dual-emitting thermometers based on rhodamine B dye-incorporated (nano) curcumin periodic mesoporous organosilicas for bioapplications.

This study explores the potential of combining periodic mesoporous organosilicas (PMOs) with a fluorescent dye to develop a ratiometric thermometry system with enhanced stability, sensitivity, and biocompatibility. PMOs, ordered porous materials known for their stability and versatility, serve as an ideal platform. Curcumin, a natural polyphenol and fluorescent dye, is incorporated into PMOs to develop curcumin-functionalized PMOs (C-PMO) and curcumin-pyrazole-functionalized PMOs (CP-PMO) via hydrolysis and co-condensation. These PMOs exhibit temperature-dependent fluorescence properties. The next step involves encapsulating rhodamine B (RhB) dye within the PMO pores to create dual-emitting PMO@dye nanocomposites, followed by a lipid bilayer (LB) coating to enhance biocompatibility and dye retention. Remarkably, within the physiological temperature range, C-PMO@RhB@LB and CP-PMO@RhB@LB demonstrate noteworthy maximum relative sensitivity (Sr) values of up to 1.69 and 2.60% K-1, respectively. This approach offers versatile means to create various ratiometric thermometers by incorporating different fluorescent dyes, holding promise for future temperature sensing applications.

Cs7Nd11(SeO3)12Cl16: first noncentrosymmetric structure among alkaline-metal lanthanide selenite halides.

Cs7Nd11(SeO3)12Cl16, the complex selenite chloride of cesium and neodymium, was synthesized in the NdOCl-SeO2-CsCl system. The compound has been characterized using single-crystal X-ray diffraction, electron diffraction, transmission electron microscopy, luminescence spectroscopy, and second-harmonic-generation techniques. Cs7Nd11(SeO3)12Cl16 crystallizes in an orthorhombic unit cell with a = 15.911(1) Å, b = 15.951(1) Å, and c = 25.860(1) Å and a noncentrosymmetric space group Pna2(1) (No. 33). The crystal structure of Cs7Nd11(SeO3)12Cl16 can be represented as a stacking of Nd11(SeO3)12 lamellas and CsCl-like layers. Because of the layered nature of the Cs7Nd11(SeO3)12Cl16 structure, it features numerous planar defects originating from occasionally missing the CsCl-like layer and violating the perfect stacking of the Nd11(SeO3)12 lamellas. Cs7Nd11(SeO3)12Cl16 represents the first example of a noncentrosymmetric structure among alkaline-metal lanthanide selenite halides. Cs7Nd11(SeO3)12Cl16 demonstrates luminescence emission in the near-IR region with reduced efficiency due to a high concentration of Nd(3+) ions causing nonradiative cross-relaxation.

A XAS study of the luminescent Eu centers in thiosilicate phosphors.

Due to its bright yellow-to-red emission, europium doped Ca2SiS4 is a very interesting material for phosphor converted light emitting diodes. The emission spectrum is highly dependent on the Eu concentration and can consist of more than one emission band. We combined X-ray absorption fine structure and photoluminescence measurements to analyze the structure of europium centers in (Ca,Eu)2SiS4 luminescent powders. This paper provides an explanation for the concentration dependency of the emission spectra. We find that at low dopant concentrations a large fraction of trivalent europium ions is unexpectedly present in the powders. These trivalent europium ions tend to form defect clusters in the luminescent powders. Furthermore we observe a preferential substitution of the europium ions over the two different substitutional Ca sites, which changes upon increasing the dopant concentration. At high dopant concentration, the powder crystallizes in the monoclinic Eu2SiS4 structure. Once more a preferential substitution of the europium ions is observed. Summarizing, the influence of the concentration on the emission spectrum is explained by a difference in preferential occupation of the Eu ions in the lattice.

Neodymium-Doped Gadolinium Compounds as Infrared Emitters for Multimodal Imaging.

This study aims to investigate the optical properties of multiple neodymium-doped gadolinium compounds as a means to examine their eligibility as optical probes for fluorescence imaging. GdVO4, GdPO4, GdAlO3, Gd2SiO5 and Gd3Ga5O12 (GGG) samples were synthesized through solid-state reactions with varying neodymium doping levels to compare their optical properties in great detail. The optimal doping concentration was generally found to be approximately 2%. Furthermore, the luminescence lifetime, which is a valuable parameter for time-gated imaging, was determined to range from 276 down to 14 µs for the highest doping concentrations, resulting from energy transfer and migration assisted decay.

Visualizing temperature inhomogeneity using thermo-responsive smart materials.

Despite the substantial progress made, the responsiveness of thermo-responsive materials upon various thermal fields is still restricted to monochromatic visualization with single-wavelength light emission. This stems from a poor understanding of the photophysical processes within the materials and the unvarying optical performance of luminescent centers' response to various ambient temperatures. Conventional techniques to assess the inhomogeneities of thermal fields can be time-consuming, require specialized equipment and suffer from inaccuracy due to the inevitable interference from background signals, especially at high temperature. To this end, we overcome these limitations for the first time, to flexibly visualize temperature inhomogeneities by developing a thermochromic smart material, SrGa12-xAlxO19:Dy3+. Two distinct modes of thermochromic properties (steady-state temperature-dependent luminescence and thermally stimulated luminescence) are investigated. It is revealed that the abundant colors (from yellow, green to red) and amazing color-changing features are due to the superior optical integration of the host (SrGa12-xAlxO19) and dopant (Dy3+) emissions under specific thermal stimulations. We suggest that this thermo-responsive smart material can be used to realize highly efficient and simple visualization of invisible thermal distribution in industry and beyond.

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization.

Covalent organic frameworks (COFs) are emerging as a new class of photoactive organic semiconductors, which possess crystalline ordered structures and high surface areas. COFs can be tailor-made toward specific (photocatalytic) applications, and the size and position of their band gaps can be tuned by the choice of building blocks and linkages. However, many types of building blocks are still unexplored as photocatalytic moieties and the scope of reactions photocatalyzed by COFs remains quite limited. In this work, we report the synthesis and application of two bipyridine- or phenylpyridine-based COFs: TpBpyCOF and TpPpyCOF. Due to their good photocatalytic properties, both materials were applied as metal-free photocatalysts for the tandem aerobic oxidation/Povarov cyclization and α-oxidation of N-aryl glycine derivatives, with the bipyridine-based TpBpyCOF exhibiting the highest activity. By expanding the range of reactions that can be photocatalyzed by COFs, this work paves the way toward the more widespread application of COFs as metal-free heterogeneous photocatalysts as a convenient alternative for commonly used homogeneous (metal-based) photocatalysts.