Enhancing deep visible-light photoelectrocatalysis with a single solid-state synthesis: Carbon nitride/TiO heterointerface.

Visible-light responsive, stable, and abundant absorbers are required for the rapid integration of green, clean, and renewable technologies in a circular economy. Photoactive solid-solid heterojunctions enable multiple charge pathways, inhibiting recombination through efficient charge transfer across the interface. This study spotlights the physico-chemical synergy between titanium dioxide (TiO) anatase and carbon nitride (CN) to form a hybrid material.

Controlling and predicting alkyl-onium electronic structure.

X-ray photoelectron spectroscopy (XPS) and calculations show that fully alkylated onium cation electronic structure can be tuned using both the alkyl chains and the central onium atom. The key for tuning the central onium atom is methyl longer alkyl chains, allowing selection of the optimum cation for a wide range of applications, including catalysis and biocides.

Monitoring the Behavior of Na Ions and Solid Electrolyte Interphase Formation at an Aluminum/Ionic Liquid Electrode/Electrolyte Interface via Operando Electrochemical X-ray Photoelectron Spectroscopy.

In electrochemical energy storage devices, the interface between the electrode and the electrolyte plays a crucial role. A solid electrolyte interphase (SEI) is formed on the electrode surface due to spontaneous decomposition of the electrolyte, which in turn controls the dynamics of ion migration during charge and discharge cycles. However, the dynamic nature of the SEI means that its chemical structure evolves over time and as a function of the applied bias; thus, a true study is extremely valuable.

Environment-Driven Variability in Absolute Band Edge Positions and Work Functions of Reduced Ceria.

The absolute band edge positions and work function (Φ) are the key electronic properties of metal oxides that determine their performance in electronic devices and photocatalysis. However, experimental measurements of these properties often show notable variations, and the mechanisms underlying these discrepancies remain inadequately understood. In this work, we focus on ceria (CeO), a material renowned for its outstanding oxygen storage capacity, and combine theoretical and experimental techniques to demonstrate environmental modifications of its ionization potential (IP) and Φ.

Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory.

Using a combination of experiments and calculations, we have gained new insights into the nature of anion-cation interactions in ionic liquids (ILs). An X-ray photoelectron spectroscopy (XPS)-derived anion-dependent electrostatic interaction strength scale, determined using XPS core-level binding energies for IL cations, is presented here for 39 different anions, with at least 18 new anions included. Linear correlations of experimental XPS core-level binding energies for IL cations with (a) calculated core binding energies (ab initio molecular dynamics (AIMD) simulations were used to generate high-quality model IL structures followed by single-point density functional theory (DFT) to obtain calculated core binding energies), (b) experimental XPS core-level binding energies for IL anions, and (c) other anion-dependent interaction strength scales led to three main conclusions.

Exploring Bismuth Coordination Complexes as Visible-Light Absorbers: Synthesis, Characterization, and Photophysical Properties.

Bismuth-based coordination complexes are advantageous over other metal complexes, as bismuth is the heaviest nontoxic element with high spin-orbit coupling and potential optoelectronics applications. Herein, four bismuth halide-based coordination complexes [BiCl(phen-thio)] (), [BiBr(phen-thio)] (), [BiI(phen-thio)] (), and [BiI(phen-Me)] () were synthesized, characterized, and subjected to detailed photophysical studies. The complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and NMR studies.

Phase Quantification of Heterogeneous Surfaces Using DFT-Simulated Valence Band Photoemission Spectra.

Quantifying the crystallographic phases present at a surface is an important challenge in fields such as functional materials and surface science. X-ray photoelectron spectroscopy (XPS) is routinely employed in surface characterization to identify and quantify chemical species through core line analysis. Valence band (VB) spectra contain characteristic but complex features that provide information on the electronic density of states (DoS) and thus can be understood theoretically using density functional theory (DFT).

Improving the biological interfacing capability of diketopyrrolopyrrole polymers p-type doping.

Polydiketopyrrolopyrrole terthiophene (DPP3T) is an organic semiconducting polymer that has been widely investigated as the active layer within organic electronic devices, such as photovoltaics and bioelectronic sensors. To facilitate interfacing between biological systems and organic semiconductors it is crucial to tune the material properties to support not only cell adhesion, but also proliferation and growth. Herein, we highlight the potential of molecular doping to judiciously modulate the surface properties of DPP3T and investigate the effects on Schwann cell behaviour on the surface.

Nanoarchitecture factors of solid electrolyte interphase formation via 3D nano-rheology microscopy and surface force-distance spectroscopy.

The solid electrolyte interphase in rechargeable Li-ion batteries, its dynamics and, significantly, its nanoscale structure and composition, hold clues to high-performing and safe energy storage. Unfortunately, knowledge of solid electrolyte interphase formation is limited due to the lack of in situ nano-characterization tools for probing solid-liquid interfaces. Here, we link electrochemical atomic force microscopy, three-dimensional nano-rheology microscopy and surface force-distance spectroscopy, to study, in situ and operando, the dynamic formation of the solid electrolyte interphase starting from a few 0.

Mixed valence Sn doped (CHNH)BiBr produced by mechanochemical synthesis.

Bismuth halides with formula ABiX, where A is an inorganic or organic cation, show desirable properties as solar absorbers and luminescent materials. Control of structural and electronic dimensionality of these compounds is important to yield materials with good light absorption and charge transport. Here we report mechanochemical reaction of (CHNH)BiBr with SnBr at room temperature in air, yielding a material with strong absorption across the visible region.

Physico-Chemical Properties of Magnetic Dicationic Ionic Liquids with Tetrahaloferrate Anions.

A series of imidazolium-based symmetrical and asymmetrical dicationic ionic liquids (DcILs) with alkyl spacers of different length and with [FeCl Br] as counter ion have been synthesized. The synthesized DcILs are characterized by using FTIR and Raman spectroscopy as well as mass spectrometry, along with single-crystal XRD analysis. Physicochemical properties such as solubility, thermal stability and magnetic susceptibility are also measured.

Computational Prediction and Experimental Realization of Earth-Abundant Transparent Conducting Oxide Ga-Doped ZnSbO.

Transparent conducting oxides have become ubiquitous in modern optoelectronics. However, the number of oxides that are transparent to visible light and have the metallic-like conductivity necessary for applications is limited to a handful of systems that have been known for the past 40 years. In this work, we use hybrid density functional theory and defect chemistry analysis to demonstrate that tri-rutile zinc antimonate, ZnSbO, is an ideal transparent conducting oxide and to identify gallium as the optimal dopant to yield high conductivity and transparency.

Degradation of Layered Oxide Cathode in a Sodium Battery: A Detailed Investigation by X-Ray Tomography at the Nanoscale.

The degradation mechanism in a sodium cell of a layered Na Al Co Ni Mn O (NCAM) cathode with P3/P2 structure is investigated by revealing the changes in microstructure and composition upon cycling. The work aims to rationalize the gradual performance decay and the alteration of the electrochemical response in terms of polarization, voltage signature, and capacity loss. Spatial reconstructions of the electrode by X-ray computed tomography at the nanoscale supported by quantitative and qualitative analyses show fractures and deformations in the cycled layered metal-oxide particles, as well as inorganic side compounds deposited on the material.

Enhanced visible light absorption in layered CsBiBr through mixed-valence Sn(ii)/Sn(iv) doping.

Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite CsBiBr, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr to the solution-phase synthesis of CsBiBr leads to substitution of up to 7% of the Bi(iii) ions by equal quantities of Sn(ii) and Sn(iv). The nature of the substitutional defects was studied by X-ray diffraction, Cs and Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations.

Experimental measurement and prediction of ionic liquid ionisation energies.

Ionic liquid (IL) valence electronic structure provides key descriptors for understanding and predicting IL properties. The ionisation energies of 60 ILs are measured and the most readily ionised valence state of each IL (the highest occupied molecular orbital, HOMO) is identified using a combination of X-ray photoelectron spectroscopy (XPS) and synchrotron resonant XPS. A structurally diverse range of cations and anions were studied.

Indium Gallium Oxide Alloys: Electronic Structure, Optical Gap, Surface Space Charge, and Chemical Trends within Common-Cation Semiconductors.

The electronic and optical properties of (InGa)O alloys are highly tunable, giving rise to a myriad of applications including transparent conductors, transparent electronics, and solar-blind ultraviolet photodetectors. Here, we investigate these properties for a high quality pulsed laser deposited film which possesses a lateral cation composition gradient (0.01 ≤ ≤ 0.

LaSrCoRhO and LaSrNiRhO:Topochemically Reduced, Mixed Valence Rh(I)/Rh(III) Oxides.

Topochemical reduction of the = 1 Ruddlesden-Popper phases LaSrCoRhO and LaSrNiRhO with Zr yields LaSrCoRhO and LaSrNiRhO, respectively. Magnetization and XPS data reveal that while the rhodium centers in LaSrCoRhO and LaSrNiRhO have an average oxidation state of Rh, these are actually mixed valence Rh(I,III) compounds, with the disproportionation of Rh driven by the favorability of locating d Rh and d Rh cations within square-planar and square-based pyramidal coordination sites, respectively.

Structure and magnetism of the Rh-containing perovskite oxides LaSrMnRhO and LaSrFeRhO.

Synchrotron X-ray powder diffraction data indicate that La0.5Sr0.5Mn0.

Demonstration of Visible Light-Activated Photocatalytic Self-Cleaning by Thin Films of Perovskite Tantalum and Niobium Oxynitrides.

Metal oxynitrides adopting the perovskite structure have been shown to be visible light-activated photocatalysts, and therefore, they have potential as self-cleaning materials where surface organic pollutants can be removed by photomineralization. In this work, we establish a route for the deposition of thin films for seven perovskite oxynitrides, CaTaON, SrTaON, BaTaON, LaTaON, EuTaON, SrNbON, and LaNbON, on quartz and alumina substrates using dip-coating of a polymer gel to form an amorphous oxide precursor film, followed by ammonolysis. The initially deposited oxide films were annealed at 800 °C, followed by ammonolysis at temperatures from 850 to 1000 °C.

Anion Distribution, Structural Distortion, and Symmetry-Driven Optical Band Gap Bowing in Mixed Halide CsSnX Vacancy Ordered Double Perovskites.

Mixed anion compounds in the vacancy ordered perovskite structure were synthesized and characterized experimentally and computationally with a focus on compounds where A = Cs. Pure anion CsSnX compounds were formed with X = Cl, Br, and I using a room temperature solution phase method. Mixed anion compounds were formed as solid solutions of CsSnCl and CsSnBr and a second series from CsSnBr and CsSnI.

Bioinspired Polymerization of Quercetin to Produce a Curcumin-Loaded Nanomedicine with Potent Cytotoxicity and Cancer-Targeting Potential in Vivo.

Nanomedicine has had a profound impact on the treatment of many diseases, especially cancer. However, synthesis of multifunctional nanoscale drug carriers often requires multistep coupling and purification reactions, which can pose major scale-up challenges. Here, we leveraged bioinspired oxidation-triggered polymerization of catechols to synthesize nanoparticles (NPs) from the plant polyphenol quercetin (QCT) loaded with a hydrophobic anticancer drug, curcumin, and functionalized with poly(ethylene glycol) (PEG) for steric stabilization in one reaction step.