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 operando study is extremely valuable. X-ray photoelectron spectroscopy (XPS) is a widely used technique to understand the surface electronic and chemical properties, but the use of ultrahigh vacuum in standard instruments is a major hurdle for their utilization in measuring wet electrochemical processes. Herein, we introduce a 3-electrode electrochemical cell to probe the behavior of Na ions and the formation of SEI at the interface of an ionic liquid (IL) electrolyte and an aluminum electrode under operando conditions. A system containing 0.5 molar NaTFSI dissolved in the IL [BMIM][TFSI] was investigated using an Al working electrode and Pt counter and reference electrodes. By optimizing the scan rate of both XPS and cyclic voltammetry (CV) techniques, we captured the formation and evolution of SEI chemistry using real-time spectra acquisition techniques. A CV scan rate of 2 mVs-1 was coupled with XPS snapshot spectra collected at 10 s per core level. The technique demonstrated here provides a platform for the chemical analysis of materials beyond batteries.

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 (CeO2), 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. Under O-deficient conditions, reduced ceria exhibits a decreased IP and Φ with significant sensitivity to defect distributions. In contrast, the IP and Φ are elevated in O-rich conditions due to the formation of surface peroxide species. Surface adsorbates and impurities can further augment these variabilities under realistic conditions. We rationalize the shifts in energy levels by separating the individual contributions from bulk and surface factors, using hybrid quantum mechanical/molecular mechanical (QM/MM) embedded-cluster and periodic density functional theory (DFT) calculations supported by interatomic-potential-based electrostatic analyses. Our results highlight the critical role of on-site electrostatic potentials in determining the absolute energy levels in metal oxides, implying a dynamic evolution of band edges under catalytic conditions.

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. First, the effect of different anions on the cation can be related to ground-state interactions. Second, the variations of anion-dependent interactions with the identity of the anion are best rationalized in terms of electrostatic interactions and not occupied valence state/unoccupied valence state interactions or polarizability-driven interactions. Therefore, the XPS-derived anion-dependent interaction strength scale can be explained using a simple electrostatic model based on electrostatic site potentials. Third, anion-probe interactions, irrespective of the identity of the probe, are primarily electrostatic, meaning that our electrostatic interaction strength scale captures some inherent, intrinsic property of anions independent of the probe used to measure the interaction strength scale.

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 [Bi2Cl6(phen-thio)2] (1), [Bi2Br6(phen-thio)2] (2), [Bi2I6(phen-thio)2] (3), and [Bi2I6(phen-Me)2] (4) 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. Spectroscopic analyses of 1-4 in solutions of different polarities were performed to understand the role of the organic and inorganic components in determining the ground- and excited-state properties of the complexes. The photophysical properties of the complexes were characterized by ground-state absorption, steady-state photoluminescence, microsecond time-resolved photoluminescence, and absorption spectroscopy. Periodic density functional theory (DFT) calculations were performed on the solid-state structures to understand the role of the organic and inorganic parts of the complexes. The studies showed that changing the ancillary ligand from chlorine (Cl) and bromine (Br) to iodine (I) bathochromically shifts the absorption band along with enhancing the absorption coefficient. Also, changing the halides (Cl, Br to I) affects the photoluminescent quantum yields of the ligand-centered (LC) emissive state without markedly affecting the lifetimes. The combined results confirmed that ground-state properties are strongly influenced by the inorganic part, and the lower-energy excited state is LC. This study paves the way to design novel bismuth coordination complexes for optoelectronic applications by rigorously choosing the ligands and bismuth salt.

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). Here, we present a method of fitting experimental photoemission spectra with DFT models for quantitative analysis of heterogeneous systems, specifically mapping the anatase to rutile ratio across the surface of mixed-phase TiO2 thin films. The results were correlated with mapped photocatalytic activity measured using a resazurin-based smart ink. This method allows large-scale functional and surface composition mapping in heterogeneous systems and demonstrates the unique insights gained from DFT-simulated spectra on the electronic structure origins of complex VB spectral features.

Solid Electrolyte Interphase Formation in Tellurium Iodide Perovskites during Electrochemistry and Photoelectrochemistry.

Halide perovskites are promising photoelectrocatalytic materials. Their further development requires understanding of surface processes during electrochemistry. Thin films of tellurium-based vacancy-ordered perovskites with formula A2TeI6, A = Cs, methylammonium (MA), were deposited onto transparent conducting substrates using aerosol-assisted chemical vapor deposition. Thin film stability as electrodes and photoelectrodes was tested in dichloromethane containing tetrabutylammonium PF6 (TBAPF6). Using photoemission spectroscopy, we show that the formation of a solid electrolyte interphase on the surface of the Cs2TeI6, consisting of CsPF6, enhances the stability of the electrode and allows extended chopped-light chronoamperometry measurements at up to 1.1 V with a photocurrent density of 16 µA/cm2. In contrast, (CH3NH3)2TeI6 does not form a passivating layer and rapidly degrades upon identical electrochemical treatment. This demonstrates the importance of surface chemistry in halide perovskite electrochemistry and photoelectrocatalysis.

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 0.1 nm thick electrical double layer to the full three-dimensional nanostructured solid electrolyte interphase on the typical graphite basal and edge planes in a Li-ion battery negative electrode. By probing the arrangement of solvent molecules and ions within the electric double layer and quantifying the three-dimensional mechanical property distribution of organic and inorganic components in the as-formed solid electrolyte interphase layer, we reveal the nanoarchitecture factors and atomistic picture of initial solid electrolyte interphase formation on graphite-based negative electrodes in strongly and weakly solvating electrolytes.

Mixed valence Sn doped (CH3NH3)3Bi2Br9 produced by mechanochemical synthesis.

Bismuth halides with formula A3Bi2X9, 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 (CH3NH3)3Bi2Br9 with SnBr2 at room temperature in air, yielding a material with strong absorption across the visible region. We attribute this to mixed valence doping of Sn(II) and Sn(IV) on the Bi site. X-Ray diffraction shows no secondary phases, even after heating at 200 °C to improve crystallinity. X-Ray photoelectron spectroscopy suggests the presence of Sn(II) and Sn(IV) states. A similar approach to dope Sn into the iodide analogue (CH3NH3)3Bi2I9 was unsuccessful.

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 [FeCl3 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. These compounds show low melting points, good solubility in water and organic solvents, thermal stability, and paramagnetism. The products of molar susceptibility and temperature (χmol ⋅T) for the synthesized DcILs have been found between 4.05 to 4.79 emu mol-1 K Oe-1 and effective magnetic moment values have also been determined to be compared to that expected from the spin-only approximation.

Computational Prediction and Experimental Realization of Earth-Abundant Transparent Conducting Oxide Ga-Doped ZnSb2O6.

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, ZnSb2O6, is an ideal transparent conducting oxide and to identify gallium as the optimal dopant to yield high conductivity and transparency. To validate our computational predictions, we have synthesized both powder samples and single crystals of Ga-doped ZnSb2O6 which conclusively show behavior consistent with a degenerate transparent conducting oxide. This study demonstrates the possibility of a family of Sb(V)-containing oxides for transparent conducting oxide and power electronics applications.

Enhanced visible light absorption in layered Cs3Bi2Br9 through mixed-valence Sn(ii)/Sn(iv) doping.

Lead-free halides with perovskite-related structures, such as the vacancy-ordered perovskite Cs3Bi2Br9, are of interest for photovoltaic and optoelectronic applications. We find that addition of SnBr2 to the solution-phase synthesis of Cs3Bi2Br9 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, 133Cs and 119Sn solid state NMR, X-ray photoelectron spectroscopy and density functional theory calculations. The resulting mixed-valence compounds show intense visible and near infrared absorption due to intervalence charge transfer, as well as electronic transitions to and from localised Sn-based states within the band gap. Sn(ii) and Sn(iv) defects preferentially occupy neighbouring B-cation sites, forming a double-substitution complex. Unusually for a Sn(ii) compound, the material shows minimal changes in optical and structural properties after 12 months storage in air. Our calculations suggest the stabilisation of Sn(ii) within the double substitution complex contributes to this unusual stability. These results expand upon research on inorganic mixed-valent halides to a new, layered structure, and offer insights into the tuning, doping mechanisms, and structure-property relationships of lead-free vacancy-ordered perovskite structures.

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. The cation gave rise to the HOMO for nine of the 60 ILs presented here, meaning it is energetically more favourable to remove an electron from the cation than the anion. The influence of the cation on the anion electronic structure (and vice versa) were established; the electrostatic effects are well understood and demonstrated to be consistently predictable. We used this knowledge to make predictions of both ionisation energy and HOMO identity for a further 516 ILs, providing a very valuable dataset for benchmarking electronic structure calculations and enabling the development of models linking experimental valence electronic structure descriptors to other IL properties, e.g. electrochemical stability. Furthermore, we provide design rules for the prediction of the electronic structure of ILs.

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

The electronic and optical properties of (InxGa1-x)2O3 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 ≤ x ≤ 0.82) and three crystallographic phases (monoclinic, hexagonal, and bixbyite). The optical gaps over this composition range are determined, and only a weak optical gap bowing is found (b = 0.36 eV). The valence band edge evolution along with the change in the fundamental band gap over the composition gradient enables the surface space-charge properties to be probed. This is an important property when considering metal contact formation and heterojunctions for devices. A transition from surface electron accumulation to depletion occurs at x ∼ 0.35 as the film goes from the bixbyite In2O3 phase to the monoclinic ß-Ga2O3 phase. The electronic structure of the different phases is investigated by using density functional theory calculations and compared to the valence band X-ray photoemission spectra. Finally, the properties of these alloys, such as the n-type dopability of In2O3 and use of Ga2O3 as a solar-blind UV detector, are understood with respect to other common-cation compound semiconductors in terms of simple chemical trends of the band edge positions and the hydrostatic volume deformation potential.

LaSrCo0.5Rh0.5O3.25 and LaSrNi0.5Rh0.5O3.25:Topochemically Reduced, Mixed Valence Rh(I)/Rh(III) Oxides.

Topochemical reduction of the n = 1 Ruddlesden-Popper phases LaSrCo0.5Rh0.5O4 and LaSrNi0.5Rh0.5O4 with Zr yields LaSrCo0.5Rh0.5O3.25 and LaSrNi0.5Rh0.5O3.25, respectively. Magnetization and XPS data reveal that while the rhodium centers in LaSrCo0.5Rh0.5O3.25 and LaSrNi0.5Rh0.5O3.25 have an average oxidation state of Rh2+, these are actually mixed valence Rh(I,III) compounds, with the disproportionation of Rh2+ driven by the favorability of locating d8 Rh1+ and d6 Rh3+ cations within square-planar and square-based pyramidal coordination sites, respectively.

Structure and magnetism of the Rh4+-containing perovskite oxides La0.5Sr0.5Mn0.5Rh0.5O3 and La0.5Sr0.5Fe0.5Rh0.5O3.

Synchrotron X-ray powder diffraction data indicate that La0.5Sr0.5Mn0.5Rh0.5O3 and La0.5Sr0.5Fe0.5Rh0.5O3 adopt distorted perovskite structures (space group Pnma) with A-site and B-site cation disorder. A combination of XPS and 57Fe Mössbauer data indicate the transition metal cations in the two phases adopt Mn3+/Rh4+ and Fe3+/Rh4+ oxidation state combinations respectively. Transport data indicate both phases are insulating, with ρ vs. T dependences consistent with 3D variable-range hopping. Magnetisation data reveal that La0.5Sr0.5Mn0.5Rh0.5O3 adopts a ferromagnetic state below Tc ∼ 60 K, which is rationalized on the basis of coupling via a dynamic Jahn-Teller distortion mechanism. In contrast, magnetic data reveal La0.5Sr0.5Fe0.5Rh0.5O3 undergoes a transition to a spin-glass state at T ∼ 45 K, attributed to frustration between nearest-neighbour Fe-Rh and next-nearest-neighbour Fe-Fe couplings.

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, CaTaO2N, SrTaO2N, BaTaO2N, LaTaON2, EuTaO2N, SrNbO2N, and LaNbON2, 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. The perovskite oxynitride thin films were characterized using XRD and EDX, with band gaps determined using Tauc plots derived from UV-vis spectroscopic data. A cobalt oxide co-catalyst was deposited onto each film by drop casting, and the photocatalytic activity assessed under visible light using dichloroindophenol dye degradation in the presence of a sacrificial oxidant. The light source used was a solar simulator equipped with a 400 nm cut-off filter. The dye degradation test demonstrated photocatalytic activity in all samples except EuTaO2N and BaTaO2N. The three most active samples were SrNbO2N, CaTaO2N, and SrTaO2N. The cobalt oxide loading was optimized for these three films and found to be 0.3 µg cm-2. Further, catalytic tests were conducted using stearic acid degradation, and this found the film of SrNbO2N with the cobalt oxide co-catalyst to be the most active for complete mineralization of this model pollutant.

Electron spectroscopy of ionic liquids: experimental identification of atomic orbital contributions to valence electronic structure.

The atomic contributions to valence electronic structure for 37 ionic liquids (ILs) are identified using a combination of variable photon energy XPS, resonant Auger electron spectroscopy (RAES) and a subtraction method. The ILs studied include a diverse range of cationic and anionic structural moieties. We introduce a new parameter for ILs, the energy difference between the energies of the cationic and anionic highest occupied fragment orbitals (HOFOs), which we use to identify the highest occupied molecular orbital (HOMO). The anion gave rise to the HOMO for 25 of the 37 ILs studied here. For 10 of the ILs, the energies of the cationic and anionic HOFOs were the same (within experimental error); therefore, it could not be determined whether the HOMO was from the cation or the anion. For two of the ILs, the HOMO was from the cation and not from the anion; consequently it is energetically more favourable to remove an electron from the cation than the anion for these two ILs. In addition, we used a combination of area normalisation and subtraction of XP spectra to produce what are effectively XP spectra for individual ions; this was achieved for 10 cations and 14 anions.

Nucleobase pairing and photodimerization in a biologically derived metal-organic framework nanoreactor.

Biologically derived metal-organic frameworks (bio-MOFs) are of great importance as they can be used as models for bio-mimicking and in catalysis, allowing us to gain insights into how large biological molecules function. Through rational design, here we report the synthesis of a novel bio-MOF featuring unobstructed Watson-Crick faces of adenine (Ade) pointing towards the MOF cavities. We show, through a combined experimental and computational approach, that thymine (Thy) molecules diffuse through the pores of the MOF and become base-paired with Ade. The Ade-Thy pair binding at 40-45% loading reveals that Thy molecules are packed within the channels in a way that fulfill both the Woodward-Hoffmann and Schmidt rules, and upon UV irradiation, Thy molecules dimerize into Thy<>Thy. This study highlights the utility of accessible functional groups within the pores of MOFs, and their ability to 'lock' molecules in specific positions that can be subsequently dimerized upon light irradiation, extending the use of MOFs as nanoreactors for the synthesis of molecules that are otherwise challenging to isolate.

Solvothermal water-diethylene glycol synthesis of LiCoPO4 and effects of surface treatments on lithium battery performance.

Olivine-structured LiCoPO4 is prepared via a facile solvothermal synthesis, using various ratios of water/diethylene glycol co-solvent, followed by thermal treatment under Ar, air, 5%H2/N2 or NH3. The diethylene glycol plays an important role in tailoring the particle size of LiCoPO4. It is found that using a ratio of water/diethylene glycol of 1 : 6 (v/v), LiCoPO4 is obtained with a homogenous particle size of ∼150 nm. The bare LiCoPO4 prepared after heating in Ar exhibits high initial discharge capacity of 147 mA h g-1 at 0.1C with capacity retention of 70% after 40 cycles. This is attributed to the enhanced electronic conductivity of LiCoPO4 due to the presence of Co2P after firing under Ar. The effects of carbon, TiN and RuO2 coating are also examined. Contrary to other studies, it is found that the solvothermally synthesised LiCoPO4 samples produced here do not require conductive coatings to achieve good performance.