Designing Atomic Interface in Sb2 S3 /CdS Heterojunction for Efficient Solar Water Splitting.

In the emerging Sb2 S3 -based solar energy conversion devices, a CdS buffer layer prepared by chemical bath deposition is commonly used to improve the separation of photogenerated electron-hole pairs. However, the cation diffusion at the Sb2 S3 /CdS interface induces detrimental defects but is often overlooked. Designing a stable interface in the Sb2 S3 /CdS heterojunction is essential to achieve high solar energy conversion efficiency. As a proof of concept, this study reports that the modification of the Sb2 S3 /CdS heterojunction with an ultrathin Al2 O3 interlayer effectively suppresses the interfacial defects by preventing the diffusion of Cd2+ cations into the Sb2 S3 layer. As a result, a water-splitting photocathode based on Ag:Sb2 S3 /Al2 O3 /CdS heterojunction achieves a significantly improved half-cell solar-to-hydrogen efficiency of 2.78% in a neutral electrolyte, as compared to 1.66% for the control Ag:Sb2 S3 /CdS device. This work demonstrates the importance of designing atomic interfaces and may provide a guideline for the fabrication of high-performance stibnite-type semiconductor-based solar energy conversion devices.

Structure and Population of Complex Ionic Species in FeCl2 Aqueous Solution by X-ray Absorption Spectroscopy.

Technologies for mass production require cheap and abundant materials such as ferrous chloride (FeCl2). The literature survey shows the lack of experimental studies to validate theoretical conclusions related to the population of ionic Fe-species in the aqueous FeCl2 solution. Here, we present an in situ X-ray absorption study of the structure of the ionic species in the FeCl2 aqueous solution at different concentrations (1-4 molL-1) and temperatures (25-80 °C). We found that at low temperature and low FeCl2 concentration, the octahedral first coordination sphere around Fe is occupied by one Cl ion at a distance of 2.33 (±0.02) Å and five water molecules at a distance of 2.095 (±0.005) Å. The structure of the ionic complex gradually changes with an increase in temperature and/or concentration. The apical water molecule is substituted by a chlorine ion to yield a neutral Fe[Cl2(H2O)4]0. The observed substitutional mechanism is facilitated by the presence of the intramolecular hydrogen bonds as well as entropic reasons. The transition from the single charged Fe[Cl(H2O)5]+ to the neutral Fe[Cl2(H2O)4]0 causes a significant drop in the solution conductivity, which well correlates with the existing conductivity models.

The Finite Size Effects and Two-State Paradigm of Protein Folding.

The coil to globule transition of the polypeptide chain is the physical phenomenon behind the folding of globular proteins. Globular proteins with a single domain usually consist of about 30 to 100 amino acid residues, and this finite size extends the transition interval of the coil-globule phase transition. Based on the pedantic derivation of the two-state model, we introduce the number of amino acid residues of a polypeptide chain as a parameter in the expressions for two cooperativity measures and reveal their physical significance. We conclude that the k2 measure, defined as the ratio of van 't Hoff and calorimetric enthalpy is related to the degeneracy of the denatured state and describes the number of cooperative units involved in the transition; additionally, it is found that the widely discussed k2=1 is just the necessary condition to classify the protein as the two-state folder. We also find that Ωc, a quantity not limited from above and growing with system size, is simply proportional to the square of the transition interval. This fact allows us to perform the classical size scaling analysis of the coil-globule phase transition. Moreover, these two measures are shown to describe different characteristics of protein folding.

Polymer nanoparticle sizes from dynamic light scattering and size exclusion chromatography: the case study of polysilanes.

Dynamic light scattering (DLS) and size exclusion chromatography (SEC) are among the most popular methods for determining polymer sizes in solution. Taking dendritic and network polysilanes as a group of least soluble polymer substances, we critically compare and discuss the difference between nanoparticle sizes, obtained by DLS and SEC. Polymer nanoparticles are typically in poor solution conditions below the theta point and are therefore in the globular conformation. The determination of particle sizes in the presence of attractive interactions is not a trivial task. The only possibility to measure, aggregation-free, the true molecular size of polymer nanoparticles in such a solution regime, is to perform the experiment with a dilute solution of globules (below the theta point and above the miscibility line). Based on the results of our polysilane measurements, we come to a conclusion that DLS provides more reliable results than SEC for dilute solutions of globules. General implications for the size measurements of polymer nanoparticles in solution are discussed.

Efficient room temperature hydrogen sensor based on UV-activated ZnO nano-network.

Room temperature hydrogen sensors were fabricated from Au embedded ZnO nano-networks using a 30 mW GaN ultraviolet LED. The Au-decorated ZnO nano-networks were deposited on a SiO2/Si substrate by a chemical vapour deposition process. X-ray diffraction (XRD) spectrum analysis revealed a hexagonal wurtzite structure of ZnO and presence of Au. The ZnO nanoparticles were interconnected, forming nano-network structures. Au nanoparticles were uniformly distributed on ZnO surfaces, as confirmed by FESEM imaging. Interdigitated electrodes (IDEs) were fabricated on the ZnO nano-networks using optical lithography. Sensor performances were measured with and without UV illumination, at room temperate, with concentrations of hydrogen varying from 5 ppm to 1%. The sensor response was found to be ∼21.5% under UV illumination and 0% without UV at room temperature for low hydrogen concentration of 5 ppm. The UV-photoactivated mode enhanced the adsorption of photo-induced O- and O2- ions, and the d-band electron transition from the Au nanoparticles to ZnO-which increased the chemisorbed reaction between hydrogen and oxygen. The sensor response was also measured at 150 °C (without UV illumination) and found to be ∼18% at 5 ppm. Energy efficient low cost hydrogen sensors can be designed and fabricated with the combination of GaN UV LEDs and ZnO nanostructures.

Visible-light photoactivity of Bi-pyrochlores with high Fe contents.

Three Bi-pyrochlores with different Fe contents (Bi(2)Ti(2)O(7), Bi(1.65)Nb(1.12)Fe(1.16)O(7) and Bi(1.9)Te(0.58)Fe(1.52)O(6.87)) were synthesized in the form of nanopowders with similar morphological characteristics. All three nanopowders show an intensive visible-light photocatalytic activity. The analysis of their band gap and absorption characteristics has shown a strong correlation with the Fe-content indicating that a significant band gap reduction can be obtained by Fe incorporation. The photocatalytic activity has not followed this trend. The initial increase in the Fe-content has resulted in a significant enhancement of the photoactivity while with the further increase the photoactivity has slowly decreased. The reason for this behaviour has been proposed to be in an opposing influence of the increased exciton density and recombination rate.

Back to the future with emerging iron technologies.

Here is a comprehensive overview of iron's potential in low-carbon energy technologies, exploring applications like metal fuel combustion, iron-based batteries, and energy-carrier cycles, as well as sustainable approaches for production and recycling with a focus on reducing environmental impact. Iron, with its abundance, safety, and electrochemical characteristics, is a promising material to contribute to a decarbonized future. This paper discusses the advancements and challenges in iron-based energy storage technologies and sustainable iron production methods. Various innovative approaches are explored as energy storage solutions based on iron, like advancements in thermochemical Fe-Cl cycles highlight the potential of iron chloride electrochemical cycles for long-term high-capacity energy storage technology. Additionally, the utilization of iron as a circular fuel in industrial processes demonstrates its potential in large-scale thermal energy generation. Sustainable iron production methods, such as electrolysis of iron chloride or oxide and deep eutectic solvent extraction, are investigated to reduce the carbon footprint in the iron and steel industry. These findings also show the importance of policy and technology improvements that are vital for the widespread use and recycling of iron-based tech, stressing the need for collaboration toward a sustainable future.

Ba4Ta2O9 oxide prepared from an oxalate-based molecular precursor-characterization and properties.

A novel heterometallic oxalate-based compound, {Ba2(H2O)5[TaO(C2O4)3]HC2O4}·H2O (1), was obtained by using an (oxalato)tantalate(V) aqueous solution as a source of the complex anion and characterized by X-ray single-crystal diffraction, IR spectroscopy, and thermal analysis. Compound 1 is a three-dimensional (3D) coordination polymer with the Ta atom connected to eight neighboring Ba atoms through the oxalate ligands and the oxo oxygen group. Thermal treatment of 1 up to 1200 °C leads to molecular precursor-to-material conversion that yields the mixed-metal γ-Ba4Ta2O9 phase. This high-temperature γ-Ba4Ta2O9 polymorph has the 6H-perovskite structure (space group P6(3)/m), in which the Ta2O9 face-sharing octahedral dimers are interconnected via corners to the regular BaO6 octahedra. To date, γ-Ba4Ta2O9 has never been obtained at room temperature, because of the reduction of symmetry (P6(3)/m → P2(1)/c) that usually occurs during the cooling. Spectroscopic, optical, photocatalytic, and electrical properties of the obtained γ-Ba4Ta2O9 phase were investigated. In addition to the experimental data, an absorption spectrum and band structure of the γ-Ba4Ta2O9 polymorph were calculated using density functional theory.

The Role of Lattice Defects on the Optical Properties of TiO2 Nanotube Arrays for Synergistic Water Splitting.

In this study, we report a facile one-step chemical method to synthesize reduced titanium dioxide (TiO2) nanotube arrays (NTAs) with point defects. Treatment with NaBH4 introduces oxygen vacancies (OVs) in the TiO2 lattice. Chemical analysis and optical studies indicate that the OV density can be significantly increased by changing reduction time treatment, leading to higher optical transmission of the TiO2 NTAs and retarded carrier recombination in the photoelectrochemical process. A cathodoluminescence (CL) study of reduced TiO2 (TiO2-x) NTAs revealed that OVs contribute significantly to the emission bands in the visible range. It was found that the TiO2 NTAs reduced for a longer duration exhibited a higher concentration of OVs. A typical CL spectrum of TiO2 was deconvoluted to four Gaussian components, assigned to F, F+, and Ti3+ centers. X-ray photoelectron spectroscopy measurements were used to support the change in the surface chemical bonding and electronic valence band position in TiO2. Electron paramagnetic resonance spectra confirmed the presence of OVs in the TiO2-x sample. The prepared TiO2-x NTAs show an enhanced photocurrent for water splitting due to pronounced light absorption in the visible region, enhanced electrical conductivity, and improved charge transportation.

Nitroreductase-sensitive fluorescent covalent organic framework for tumor hypoxia imaging in cells.

Covalent organic frameworks (COFs) have been used in cell imaging, but very rarely for imaging specific cell conditions. Herein, a ß-ketoenamine-based fluorescent COF was post-synthetically modified to incorporate a hypoxia-targeting molecule. Fluorescence microscopy imaging shows that the material discriminates between HeLa cells grown under hypoxia and those cultured under normoxia.

Silica Coated Bi2Se3 Topological Insulator Nanoparticles: An Alternative Route to Retain Their Optical Properties and Make Them Biocompatible.

Localized surface plasmon resonance (LSPR) is the cause of the photo-thermal effect observed in topological insulator (TI) bismuth selenide (Bi2Se3) nanoparticles. These plasmonic properties, which are thought to be caused by its particular topological surface state (TSS), make the material interesting for application in the field of medical diagnosis and therapy. However, to be applied, the nanoparticles have to be coated with a protective surface layer, which prevents agglomeration and dissolution in the physiological medium. In this work, we investigated the possibility of using silica as a biocompatible coating for Bi2Se3 nanoparticles, instead of the commonly used ethylene-glycol, which, as is presented in this work, is not biocompatible and alters/masks the optical properties of TI. We successfully prepared Bi2Se3 nanoparticles coated with different silica layer thicknesses. Such nanoparticles, except those with a thick, ≈200 nm silica layer, retained their optical properties. Compared to ethylene-glycol coated nanoparticles, these silica coated nanoparticles displayed an improved photo-thermal conversion, which increased with the increasing thickness of the silica layer. To reach the desired temperatures, a 10-100 times lower concentration of photo-thermal nanoparticles was needed. In vitro experiments on erythrocytes and HeLa cells showed that, unlike ethylene glycol coated nanoparticles, silica coated nanoparticles are biocompatible.

Saturation magnetisation as an indicator of the disintegration of barium hexaferrite nanoplatelets during the surface functionalisation.

Barium hexaferrite nanoplatelets (BHF NPLs) are permanent nanomagnets with the magnetic easy axis aligned perpendicular to their basal plane. By combining this specific property with optimised surface chemistry, novel functional materials were developed, e.g., ferromagnetic ferrofluids and porous nanomagnets. We compared the interaction of chemically different phosphonic acids, hydrophobic and hydrophilic with 1-4 phosphonic groups, with BHF NPLs. A decrease in the saturation magnetisation after functionalising the BHF NPLs was correlated with the mass fraction of the nonmagnetic coating, whereas the saturation magnetisation of the NPLs coated with a tetraphosphonic acid at 80 °C was significantly lower than expected. We showed that such a substantial decrease in the saturation magnetisation originates from the disintegration of BHF NPLs, which was observed with atomic-resolution scanning transmission electron microscopy and confirmed by a computational study based on state-of-the-art first-principles calculations. Fe K-edge XANES (X-ray absorption near-edge structure) and EXAFS (Extended X-ray absorption fine structure) combined with Fourier-transformed infrared (FTIR) spectroscopy confirmed the formation of an Fe-phosphonate complex on the partly decomposed NPLs. Comparing our results with other functionalised magnetic nanoparticles confirmed that saturation magnetisation can be exploited to identify the disintegration of magnetic nanoparticles when insoluble disintegration products are formed.

Non-covalent ligand-oxide interaction promotes oxygen evolution.

Strategies to generate high-valence metal species capable of oxidizing water often employ composition and coordination tuning of oxide-based catalysts, where strong covalent interactions with metal sites are crucial. However, it remains unexplored whether a relatively weak "non-bonding" interaction between ligands and oxides can mediate the electronic states of metal sites in oxides. Here we present an unusual non-covalent phenanthroline-CoO2 interaction that substantially elevates the population of Co4+ sites for improved water oxidation. We find that phenanthroline only coordinates with Co2+ forming soluble Co(phenanthroline)2(OH)2 complex in alkaline electrolytes, which can be deposited as amorphous CoOxHy film containing non-bonding phenanthroline upon oxidation of Co2+ to Co3+/4+. This in situ deposited catalyst demonstrates a low overpotential of 216 mV at 10 mA cm-2 and sustainable activity over 1600 h with Faradaic efficiency above 97%. Density functional theory calculations reveal that the presence of phenanthroline can stabilize CoO2 through the non-covalent interaction and generate polaron-like electronic states at the Co-Co center.

Self-adaptive amorphous CoOxCly electrocatalyst for sustainable chlorine evolution in acidic brine.

Electrochemical chlorine evolution reaction is of central importance in the chlor-alkali industry, but the chlorine evolution anode is largely limited by water oxidation side reaction and corrosion-induced performance decay in strong acids. Here we present an amorphous CoOxCly catalyst that has been deposited in situ in an acidic saline electrolyte containing Co2+ and Cl- ions to adapt to the given electrochemical condition and exhibits ~100% chlorine evolution selectivity with an overpotential of ~0.1 V at 10 mA cm-2 and high stability over 500 h. In situ spectroscopic studies and theoretical calculations reveal that the electrochemical introduction of Cl- prevents the Co sites from charging to a higher oxidation state thus suppressing the O-O bond formation for oxygen evolution. Consequently, the chlorine evolution selectivity has been enhanced on the Cl-constrained Co-O* sites via the Volmer-Heyrovsky pathway. This study provides fundamental insights into how the reactant Cl- itself can work as a promoter toward enhancing chlorine evolution in acidic brine.

Cationic Covalent Organic Polymer Thin Film for Label-free Electrochemical Bacterial Cell Detection.

Numerous species of bacteria pose a serious threat to human health and cause several million deaths annually. It is therefore essential to have quick, efficient, and easily operable methods of bacterial cell detection. Herein, we synthesize a novel cationic covalent organic polymer (COP) named CATN through the Menshutkin reaction and evaluate its potential as an impedance sensor for Escherichia coli cells. On account of its positive surface charge (ζ-potential = +21.0 mV) and pyridinium moieties, CATN is expected to interact favorably with bacteria that possess a negatively charged cell surface through electrostatic interactions. The interdigitated electrode arrays were coated with CATN using a simple yet non-traditional method of electrophoresis and then used in two-electrode electrochemical impedance spectroscopy (EIS) measurements. The impedance response showed a linear relationship with the increasing concentration of E. coli. The system was sensitive to bacterial concentrations as low as ∼30 CFU mL-1, which is far below the concentration considered to cause illnesses. The calculated limit of detection was as low as 2 CFU mL-1. This work is a rare example of a COP used in this type of bacteria sensing and is anticipated to stimulate further interest in the synthesis of organic polymers for EIS-based sensors.

Implicit water model within the Zimm-Bragg approach to analyze experimental data for heat and cold denaturation of proteins.

Studies of biopolymer conformations essentially rely on theoretical models that are routinely used to process and analyze experimental data. While modern experiments allow study of single molecules in vivo, corresponding theories date back to the early 1950s and require an essential update to include the recent significant progress in the description of water. The Hamiltonian formulation of the Zimm-Bragg model we propose includes a simplified, yet explicit model of water-polypeptide interactions that transforms into the equivalent implicit description after performing the summation of solvent degrees of freedom in the partition function. Here we show that our model fits very well to the circular dichroism experimental data for both heat and cold denaturation and provides the energies of inter- and intra-molecular H-bonds, unavailable with other processing methods. The revealed delicate balance between these energies determines the conditions for the existence of cold denaturation and thus clarifies its absence in some proteins.

Covalent Organic Polymers and Frameworks for Fluorescence-Based Sensors.

Following the advancements and diversification in synthetic strategies for porous covalent materials in the literature, the materials science community started to investigate the performance of covalent organic polymers (COPs) and covalent organic frameworks (COFs) in applications that require large surface areas for interaction with other molecules, chemical stability, and insolubility. Sensorics is an area where COPs and COFs have demonstrated immense potential and achieved high levels of sensitivity and selectivity on account of their tunable structures. In this review, we focus on those covalent polymeric systems that use fluorescence spectroscopy as a method of detection. After briefly reviewing the physical basis of fluorescence-based sensors, we delve into various kinds of analytes that have been explored with COPs and COFs, namely, heavy metal ions, explosives, biological molecules, amines, pH, volatile organic compounds and solvents, iodine, enantiomers, gases, and anions. Throughout this work, we discuss the mechanisms involved in each sensing application and aim to quantify the potency of the discussed sensors by providing limits of detection and quenching constants when available. This review concludes with a summary of the surveyed literature and raises a few concerns that should be addressed in the future development of COP and COF fluorescence-based sensors.

Enhancing the Mechanical Properties of Biodegradable Mg Alloys Processed by Warm HPT and Thermal Treatments.

In this study, several biodegradable Mg alloys (Mg5Zn, Mg5Zn0.3Ca, Mg5Zn0.15Ca, and Mg5Zn0.15Ca0.15Zr, numbers in wt%) were investigated after thermomechanical processing via high-pressure torsion (HPT) at elevated temperature as well as after additional heat treatments. Indirect and direct analyses of microstructure revealed that the significant strength increases arise not only from dislocations and precipitates but also from vacancy agglomerates. By contrast with former low-temperature processing routes applied by the authors, a significant ductility was obtained because of temperature-induced dynamic recovery. The low initial values of Young's modulus were not significantly affected by warm HPT-processing. nor by heat treatments afterwards. Also, corrosion resistance did not change or even increase during those treatments. Altogether, the study reveals a viable processing route for the optimization of Mg alloys to provide enhanced mechanical properties while leaving the corrosion properties unaffected, suggesting it for the use as biodegradable implant material.

Oxygen Vacancy-Related Cathodoluminescence Quenching and Polarons in CeO2.

We used cathodoluminescence (CL) spectroscopy to characterize the oxygen vacancies (VO) in ceria (CeO2). The effects of the processing atmosphere and thermal quenching temperature on the nature and distribution of the intrinsic defects and on the spectroscopic behavior were investigated. The presence of polarons and associates of the polarons with the oxygen vacancies such as (VO ••-CeCe ')• is demonstrated. CL intensity quenching above a critical concentration of VO has been shown. Even though the emission centers in all samples are the same, their concentration changes with the oxygen partial pressure of the processing atmosphere. Deconvolution of the observed CL spectra shows that the emissions originating from the F0 centers prevail over those of F+ centers of VO when the defect concentration is high.

Formation of Fe(III)-phosphonate Coatings on Barium Hexaferrite Nanoplatelets for Porous Nanomagnets.

Amorphous coatings formed with mono-, di-, and tetra-phosphonic acids on barium hexaferrite (BHF) nanoplatelets using various synthesis conditions. The coatings, synthesized in water with di- or tetra-phosphonic acids, were thicker than that could be expected from the ligand size and the surface coverage, as determined by thermogravimetric analysis. Here, we propose a mechanism for coating formation based on direct evidence of the surface dissolution/precipitation of the BHF nanoplatelets. The partial dissolution of the nanoplatelets was observed with atomic-resolution scanning transmission electron microscopy, and the released Fe(III) ions were detected with energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy in amorphous coating. The strong chemical interaction between the surface Fe(III) ions with phosphonic ligands induces the dissolution of BHF nanoplatelets and the consequent precipitation of the Fe(III)-phosphonates that assemble into a porous coating. The so-obtained porous nanomagnets are highly responsive to a very weak magnetic field (in the order of Earth's magnetic field) at room temperature, which is a major advantage over the classic mesoporous nanomaterials and metal-organo-phosphonic frameworks with only a weak magnetic response at a few kelvins. The combination of porosity with the intrinsic magneto-crystalline anisotropy of BHF can be exploited, for example, as sorbents for heavy metals from contaminated water.