Mixed-anion Compounds Research Articles

Iron-Based Layered Perovskite Oxyfluoride Electrocatalyst for Oxygen Evolution: Insights from Crystal Facets with Heteroanionic Coordination.

Mixed-anion compounds have recently attracted attention as solid-state materials that exhibit properties unattainable with those of their single-anion counterparts. However, the use of mixed-anion compounds to control the morphology and engineer the crystal facets of electrocatalysts has been limited because their synthesis method is still immature. This study explored the electrocatalytic properties of a Pb-Fe oxyfluoride, Pb3Fe2O5F2, with a layered perovskite structure for oxygen evolution reaction (OER) and compared its properties in detail with those of a bulk-type cubic three-dimensional (3D) perovskite, PbFeO2F. A Pb3Fe2O5F2 electrode prepared with carbon nanotubes and a graphite sheet as a conductive support and a substrate, respectively, demonstrated better OER performance than a PbFeO2F electrode. The role of specific crystal facets of Pb3Fe2O5F2 in enhancing the OER activity was elucidated through electrochemical analysis. Density functional theory calculations indicated that the Pb3Fe2O5F2 (060) facet with Fe sites exhibited a lower theoretical overpotential for the OER, which was attributed to a moderately strong interaction between the active sites and the reaction intermediates; this interaction was reinforced by the strong electron-withdrawing behavior of fluoride ions. This finding offers new insights for developing efficient electrocatalysts based on oxyfluorides, leveraging the high electronegativity of fluorine to optimize the electronic states at active sites for the OER, without relying on precious metals.

Lone Pair Induced 1D Character and Weak Cation-Anion Interactions: Two Ingredients for Low Thermal Conductivity in Mixed-Anion Metal Chalcohalide CuBiSCl2.

Mixed-anion compounds, which incorporate multiple types of anions into materials, display tailored crystal structures and physical/chemical properties, garnering immense interest in various applications such as batteries, catalysis, photovoltaics, and thermoelectrics. However, detailed studies regarding correlations among crystal structure, chemical bonding, and thermal/vibrational properties are rare for these compounds, which limits the exploration of mixed-anion compounds for associated thermal applications. In this work, we investigate the lattice dynamics and thermal transport properties of the metal chalcohalide, CuBiSCl2. A high-purity polycrystalline CuBiSCl2 sample exhibits a low lattice thermal conductivity (κL) of 0.9-0.6 W/(m·K) from 300 to 573 K. By combining various experimental techniques, including three-dimensional (3D) electron diffraction, with theoretical calculations, we elucidate the origin of low κL in CuBiSCl2. The stereochemical activity of the 6s2 lone pair of Bi3+ favors an asymmetric environment with neighboring anions involving both short and long bond lengths. This particularity often implies weak bonding, low structure dimensionality, and strong anharmonicity, leading to a low κL. In addition, the strong 2-fold linear S-Cu-S coordination with weak Cu···Cl interactions induces a large anisotropic vibration of Cu, which enables strong phonon-phonon scattering and decreases κL. The investigations into lattice dynamics and thermal transport properties of CuBiSCl2 broaden the scope of the existing mixed-anion compounds suitable for the associated thermal applications, offering a new avenue for the search for low thermal conductivity materials in low-cost mixed-anion compounds.

In Situ Single-phase Formation of LaCl(CN2) Mixed-Anion Compound Via Controlled Pyrolysis of La3+ Modified Melamine Precursor.

Nitride (N3-) or cyanamide (CN22-) based mixed-anion compounds stand as attractive materials due to their unique properties derived from the binary or multiple anions, although their synthesis remains challenging in incorporating the N3- or CN22- anions safely. This work highlights the first demonstration of in situ single phase formation of a LaCl(CN2) mixed-anion compound from a stable single source precursor, melamine modified with LaCl3 preparable under aqueous conditions. The in situ formation of LaCl(CN2) involves the chemical modification of melamine with LaCl3 to form a complex. Upon heating of the precursor under N2 flowing, this complex generates cyanamide species around 400 °C, which react with LaCl3 and nonsublimated melamine to afford a binary LaCl(CN2)/g-C3N4 composite. Further pyrolysis at 800 °C decomposes the g-C3N4 counterpart, resulting in the LaCl(CN2) single-phase formation. The electronic properties of the precursor-derived single phase LaCl(CN2) were studied by the density functional theory calculation and UV-vis spectroscopy combined with X-ray photoelectron spectroscopy analyses and characterized by measuring 4.7, 1.8, and -2.9 eV for the band gap energy, the valence band maximum, and the conduction band minimum relative to Fermi energy, respectively. This study paves the way for exploring various cyanamide-based mixed anion compounds, advancing their potential applications in various fields.

Single crystal growth of complex layered oxychalcogenide by melt-solidification method

We have successfully grown single crystals of layered mixed-anion compound Sr2ZnCu2Se2O2 by a simple melt-growth method. Single crystals of the layered oxychalcogenides Sr2ZnCu2Se2O2 were grown by melt-solidification of stoichiometric raw materials. Plate-like single crystals were obtained, and the maximum size of crystals was 2.5 × 1.4 mm2. Thermal analysis result indicates simple melting-solidification-like behavior, and the size of crystals increases significantly above the melting point revealed by this measurement. X-ray rocking curve (XRC) measurement results of the single crystal showed no peak splitting, with a narrow full width half maximum of 30 and 97 arcsec in (105) and (0012) peaks, respectively. The electrical conductivity of single crystals on the a(b) plane was 4.34 × 10−1 S/cm at room temperature. Obtained single crystals were transparent, and the absorption edge was observed around 560 nm in the transmittance measurement. Although layered oxychalcogenide Sr2ZnCu2Se2O2 has a complex composition and structure, this compound exhibits congruent melting behavior in a sealed environment. This feature enables us to grow single crystals of mixed-anion compounds easily by the melt-growth method.

Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances.

ConspectusSecond-order nonlinear optical (NLO) materials are currently a hot topic in modern solid-state chemistry and optics because they can produce coherent light by frequency conversion. Noncentrosymmetric (NCS) structure is not only the prerequisite for NLO materials but also a challengeable issue because materials tend to be centrosymmetric (CS) in terms of thermodynamical stability. Among NLO materials, an excellent infrared (IR) candidate should simultaneously meet several strict key conditions including a large NLO coefficient, high laser-induced damage threshold (LIDT), phase-matchable (PM) behavior, and so on. Achieving a balance between the large NLO effect and high LIDT is difficult, as they have contradictory requirements for chemical bonds. Considering the urgent need of the high-power IR laser market and the drawbacks of the available ones, exploring new high-performance IR NLO crystals is necessary while challenging. In this Account, we first briefly introduce the status and advancement of IR NLO crystals and emphasize the criteria of an excellent candidate. Then, we will introduce five simple methods developed by us to discover practical NLO candidates through understanding of the chemical composition-structure-NLO performance relationship. (1) A rarely investigated system with simple chemical compositions as new-type NLO crystals, namely, adducts containing S8 molecules, are developed. Combining a chairlike S8 unit with other units through van der Waals forces has successfully obtained several high-performance NLO adducts. (2) The main trend in exploring new NLO crystals is that the chemical composition is more and more diversified and the structure is more and more complex, and expensive and chemically active alkaline and alkaline earth metals are usually introduced as counter cations. In contrast, the research on systems with simple chemical compositions, simple structures, and low costs has been continuously ignored. The binary M2Q3 (M = Ga, In; Q = S, Se) family with rich acentric modifications has been systematically investigated, and they all exhibit strong SHG effects and high LIDTs. (3) We first proposed the concept of inducing CS structures transformed to NCS ones by partial cation substitution to design novel NLO crystals. Considering the huge number of CS structures in the database compared to the number of NCS structures, it is an attractive method to apply CS structures as the parents to obtain potential NLO materials via partial-substitution-induced symmetry breaking. A series of chalcogenides with high NLO performances have been successfully obtained by us in this way. (4) We investigated the first NLO-active rare earth (RE) chalcophosphates and developed this family systematically, and they demonstrate wonderful comprehensive NLO properties. (5) We created a novel mixed-anion system for NLO applications, namely, chalcogenide borates. Usually, mixed-anion compounds can engender a synergistic effect to obtain desired IR NLO properties. Our recent progress on this system suggests that chalcogenide borates are potential candidates for IR NLO applications, although the study is still in its infancy. Finally, we state the current problems of IR NLO materials and give some perspectives for their future development.

A brief review of characteristic luminescence properties of Eu3+ in mixed-anion compounds.

Trivalent europium (Eu3+) ions show red luminescence with sharp spectral lines owing to the intraconfigurational 4f-4f transitions. Because of their characteristic luminescence properties, various Eu3+-doped inorganic compounds have been developed to meet the demands of optoelectronic devices. Regardless of shielding by the outer 5s and 5p orbitals, the properties of the Eu3+:4f-4f transition depend on the local environment, such as the shapes of the coordination polyhedra, site symmetry, nephelauxetic effects, crystal field effects, and bonding character. Mixed-anion coordination, where multiple types of anions surround a single Eu3+ ion, can directly affect the optical properties of Eu3+. We review the luminescence properties of Eu3+ ions in mixed-anion compounds of the oxynitride YSiO2N and oxyhalides YOX (X = Cl or Br). Oxynitride and oxyhalide coordination results in characteristic transition probabilities and branching ratios of the 5D0 → 7F0-6 transitions due to distorted structural environments and red-shifted charge transfer excitation bands due to an upward shift of the valence band. The expected and experimentally observed features of Eu3+ luminescence in mixed-anion compounds are outlined based on band and Judd-Ofelt theories. Future applications of the intense red luminescence at ∼620 nm under near-ultraviolet light illumination in Eu3+-doped mixed-anion compounds are introduced, and material design guidelines for new functional Eu3+-doped phosphors are presented.

Band engineering of layered oxyhalide photocatalysts for visible-light water splitting.

The band structure offers fundamental information on electronic properties of solid state materials, and hence it is crucial for solid state chemists to understand and predict the relationship between the band structure and electronic structure to design chemical and physical properties. Here, we review layered oxyhalide photocatalysts for water splitting with a particular emphasis on band structure control. The unique feature of these materials including Sillén and Sillén-Aurivillius oxyhalides lies in their band structure including a remarkably high oxygen band, allowing them to exhibit both visible light responsiveness and photocatalytic stability unlike conventional mixed anion compounds, which show good light absorption, but frequently encounter stability issues. For band structure control, simple strategies effective in mixed-anion compounds, such as anion substitution forming high energy p orbitals in accordance with its electronegativity, is not effective for oxyhalides with high oxygen bands. We overview key concepts for band structure control of oxyhalide photocatalysts such as lone-pair interactions and electrostatic interactions. The control of the band structure of inorganic solid materials is a crucial challenge across a wide range of materials chemistry fields, and the insights obtained by the development of oxyhalide photocatalysts are expected to provide knowledge for diverse materials chemistry.

Review on synthetic approaches and PEC activity performance of bismuth binary and mixed-anion compounds for potential applications in marine engineering.

Photoelectrochemical (PEC) technology in marine engineering holds significant importance due to its potential to address various challenges in the marine environment. Currently, PEC-type applications in marine engineering offer numerous benefits, including sustainable energy generation, water desalination and treatment, photodetection, and communication. Finding novel efficient photoresponse semiconductors is of great significance for the development of PEC-type techniques in the marine space. Bismuth-based semiconductor materials possess suitable and tunable bandgap structures, high carrier mobility, low toxicity, and strong oxidation capacity, which gives them great potential for PEC-type applications in marine engineering. In this paper, the structure and properties of bismuth binary and mixed-anion semiconductors have been reviewed. Meanwhile, the recent progress and synthetic approaches were discussed from the point of view of the application prospects. Finally, the issues and challenges of bismuth binary and mixed-anion semiconductors in PEC-type photodetection and hydrogen generation are analyzed. Thus, this perspective will not only stimulate the further investigation and application of bismuth binary and mixed-anion semiconductors in marine engineering but also help related practitioners understand the recent progress and potential applications of bismuth binary and mixed-anion compounds.

Fluorosulfide La2.7Ba6.3F8.7S6 with a double-layer honeycomb structure enabling fluoride-ion conduction

Mixed-anion compounds for fluoride-ion conductors have been explored. Through a material within the BaS–LaF3–BaF2 ternary phase diagram, we discovered a novel fluorosulfide, La2.7Ba6.3F8.7S6, which exhibits fluoride-ion conduction.

(Invited) Stable Layered Oxyhalide Photocatalysts for Visible-Light-Induced Water Splitting

Water splitting using photocatalysts has attracted considerable attention for producing H2 as a clean energy carrier, while the effective utilization of visible light is imperative to achieve the desired efficiency for practical applications. Recently, mixed-anion compounds such as oxynitrides have been intensively studied as promising candidates since one can expect that higher energy p orbitals of non-oxide anions (e.g., N-2p) elevate their VBM values. Unfortunately, most of them are subject to facile self-oxidation by photogenerated holes, while highly dispersed cocatalyst particles certainly improve the stability of some oxynitrides.Recently, we have revealed that some layered perovskite oxyhalides fulfil the necessary conditions for visible-light-induced water splitting due to their unique VBMs. For example, Bi4NbO8Cl belongs to the n = 1 members of the Sillén–Aurivillius perovskite family [(Bi2O2)2X]3+[A n -1BnO3n+1]3, which is composed of fluorite [Bi2O2], perovskite [NbO4], and halogen [Cl] layers as depicted in Figure 1. DFT calculations show that the VBM mainly consists of O-2p orbitals instead of Cl-3p, but its position determined by electrochemical measurement is much more negative (ca. 2.2 V vs. SHE) than those of conventional metal oxides (ca. 3.0 V). The significantly elevated VBMs of Bi4NbO8Cl can be understood by the strong hybridization between electron-filled Bi-6s and O-2p with the help of empty Bi-6p orbitals. In addition, Madelung site potential analysis for Bi4NbO8Cl indicated that the oxygen sites in the fluorite layer were electrostatically destabilized, which also certainly contributed to the elevation of the VBM that mainly consists of O-2p. Consequently, Bi4NbO8Cl possesses both a narrow band gap (2.4 eV) for visible light absorption up to ca. 500 nm and a more negative CBM (ca.–0.2 V vs. SHE) than the water reduction potential, which were testified by the substantial generation of H2 or O2 in the presence of an electron donor or acceptor, respectively. The substantially high durability against self-oxidative deactivation was also confirmed by the long-term water splitting in a Z-scheme system in which Bi4NbO8Cl was employed as the OEP. Since O– anions are known to be relatively stable, photogenerated holes populated at the O-2p orbitals will not lead to self-oxidative decomposition but rather to the oxidation of water.More oxyhalides with various perovskite layers (n) have been explored. However, reports on the synthesis of multiple-layered (n ≥ 2) perovskites were limited, probably due to the severe conditions required for their synthesis in the conventional solid state reaction. To solve this problem, a new two-step synthesis method including polymerized complex synthesis and a “bricklaying” synthesis were developed; providing a wide variety of new oxyhalides applicable to visible-light-induced water splitting. We also demonstrate that a oxyiodides such as Ba2Bi3Nb2O11I not only has access to a wider range of visible light than its chloride and bromide counterparts, but also exhibit much higher activity due to longer lifetime of photogenerated carriers.These studies on new oxyhalide materials provide new strategies for developing stable photocatalysts for visible-light-induced water splitting by manipulating the interaction between the s orbitals of post-transition metals (e.g., Bi-6s) and O-2p orbitals in the specific crystal structure.

Two-dimensional phase-change chalcohalides

Two-dimensional (2D) materials exhibiting structural phase transitions have a wide range of potential applications, yet 2D phase-change materials have been mostly restricted to binary chalcogenides. Here, we report the computational discovery of a new class of mixed-anion 2D phase-change Janus chalcohalides InSeX (X = Cl, Br, I), in which the lateral displacements of the halogen atoms can be induced by external stimuli such as biaxial strain, electric field, or chemical vacancies, leading to a structural phase transition from an octahedrally (O) coordinated phase to a unique tetrahedrally (T) coordinated phase. The O-to-T phase transition not only leads to an indirect-to-direct bandgap transition, but also results in a drastic reduction of the electron effective mass from 0.31 to 0.81 m0 to ∼0.19 m0. These results highlight the potential for discovering novel phase-change materials in mixed-anion compounds.

Bifunctional Lead–Iron Oxyfluorides, 3D Cubic PbFeO2f and 2D Layered Pb3Fe2O5F2, Driving Photoelectrochemical and Electrochemical Water-Oxidation

Introduction Photoelectrochemical water splitting has attracted attention as a method of generating solar fuel such as hydrogen gas to be useful as a renewable energy carrier and a clean fuel of an internal‐combustion engine. For water oxidation of the half reaction in the water splitting, mixed-anion compounds have appeared as good candidates of the catalyst. In the mixed-anion compounds, a metal center is coordinated by several kind of anionic species. This environment induces their wide variety of physical and chemical properties not to be realized in single anion counterparts. The mixed-anion compounds possess visible-light responsibility and can utilize sunlight efficiently, therefore, which have fascinated photocatalyst researchers. The reason why they absorb visible light is the narrow bandgap with less electronegative anion species than oxygen. However, they are not very stable for photoelectrochemical water-oxidation because photogenerated holes oxidize the anion species except for oxygen in the compounds and cause degradation. Recently, we have reported an oxyfluoride Pb2Ti2O5.4F1.2 as a stable photoanode material that absorbs visible light at wavelengths up to ~500 nm.1 Oxyfluoride containing O2− and F− anions in the same phase is an example of the mixed-anion compounds. The other anion F− is less oxidized than O2−. Thus, the Pb2Ti2O5.4F1.2 photoanode showed essential stability toward the degradation by photogenerated holes exceptionally. However, this is the sole example of a visible-light-responsive oxyfluoride photoanode. Development of a new oxyfluoride photoanode absorbing visible light is important to gain the insight for water oxidation using the oxyfluorides. In the present work, another type of lead-iron oxyfluorides, PbFeO2F and Pb3Fe2O5F2, are applied to water oxidation as not only a photoanode but also an electrocatalyst.2,3 The lead-iron oxyfluoride, PbFeO2F, drives photoelectrochemical water-oxidation in visible light up to ~600 nm. In addition, this oxyfluoride functions as the electrocatalyst for water oxidation.2 In the electrochemical water-oxidation, another Pb3Fe2O5F2 shows higher performance for water oxidation than PbFeO2F. It seems that the crystal structure of two-dimensional layered perovskite Pb3Fe2O5F2 influences the superior performance to three-dimensional cubic perovskite PbFeO2F.3 Results and Discussion PbFeO2F and Pb3Fe2O5F2 powder were synthesized through a solid-state reaction and that in the evacuated glass tube, respectively.2,3 They were deposited on a fluorine-doped tin oxide (FTO) glass substrate by using electrophoresis method. The PbFeO2F or Pb3Fe2O5F2/FTO electrode was subjected to post-necking treatment to deposit TiO2 layer (TiO2/PbFeO2F or Pb3Fe2O5F2/FTO electrode), followed by electrodeposition of cobalt phosphate (Co-Pi) cocatalyst (Co-Pi/TiO2/PbFeO2F or Pb3Fe2O5F2/FTO electrode). Linear-sweep voltammetry for the as-prepared electrodes was conducted under intermittent visible-light irradiation (>400 nm) in 0.1 M K3PO4 solution (Figure 1A). The PbFeO2F/FTO electrode exhibited no photocurrent response. By contrast, a slight photocurrent response was observed for the TiO2/PbFeO2F/FTO electrode because of mainly improved interparticle conductivity in the electrode. Furthermore, a clear anodic photocurrent was observed for the Co-Pi/TiO2/PbFeO2F/FTO electrode. The Co-Pi cocatalyst, known as a water-oxidation promoter, improved the charge transfer at the electrode/water interface and charge separation in the electrode. Meanwhile, the Co-Pi/TiO2/PbFeO2F/FTO electrode exhibited an anodic photocurrent in visible light with longer wavelengths than ~600 nm. These tendencies were like those of Pb3Fe2O5F2 electrodes though the photocurrent were slightly higher than the PbFeO2F electrodes (Figure 1A, right). On contrary to the photoelectrochemical water-oxidation, a clear difference was observed when using those lead-iron oxyfluorides as an electrocatalyst. Under dark conditions, controlled-potential electrolysis with non-modified PbFeO2F and Pb3Fe2O5F2/FTO electrode was performed at +1.7 V vs. RHE (Figure 1B). The evolved O2 was detected by GC analysis in the measurement. The amount of that was almost one-fourth of electrons flowed during the electrolysis, which means the water oxidation was the major path for the electrochemical reaction. Besides, Pb3Fe2O5F2/FTO electrode showed 8 times higher activity than PbFeO2F. That reason has not been revealed but the difference is likely to be attributed to two-dimensional layered perovskite Pb3Fe2O5F2 and three-dimensional cubic perovskite PbFeO2F. References Hirayama, H. Nakata, H. Wakayama, S. Nishioka, T. Kanazawa, R. Kamata, Y. Ebato, K. Kato, H. Kumagai, A. Yamakata, K. Oka and K. Maeda, Solar-Driven Photoelectrochemical Water Oxidation over an n-Type Lead-Titanium Oxyfluoride Anode, J. Am. Chem. Soc., 141, 17158 (2019).Mizuochi, K. Izumi, Y. Inaguma and K. Maeda, A bifunctional lead–iron oxyfluoride, PbFeO2F, that functions as a visible-light-responsive photoanode and an electrocatalyst for water oxidation, RSC Adv., 11, 25616 (2021).Mizuochi, K. Oka, Y. Inaguma and K. Maeda, A two-dimensional perovskite oxyfluoride Pb3Fe2O5F2 as a catalyst for electrochemical oxidation of water to oxygen, Sustain. Energy Fuels, 6, 2423 (2022). Figure 1

Topochemical Anionic Subunit Insertion Reaction for Constructing Nanoparticles of Layered Oxychalcogenide Intergrowth Structures.

Intergrowth compounds contain alternating layers of chemically distinct subunits that yield composition-tunable synergistic properties. Synthesizing nanoparticles of intergrowth structures requires atomic-level intermixing of the subunits rather than segregation into stable constituent phases. Here we introduce an anionic subunit insertion reaction for nanoparticles that installs metal chalcogenide layers between metal oxide sheets. Anionic [CuS]- subunits from solution replace interlayer chloride anions from LaOCl to form LaOCuS topochemically with retention of crystal structure and morphology. Sodium acetylacetonate helps extract Cl- concomitant with the insertion of S2- and Cu+ and is generalized to other oxychalcogenides. This topochemical reaction produces nanoparticles of ordered mixed-anion intergrowth compounds and expands nanoparticle ion exchange chemistry to anionic subunits.

Evolutionary Algorithm Directed Synthesis of Mixed Anion Compounds LaF2X (X = Br, I) and LaFI2.

Mixed-anion compounds have attracted growing attentions, but their synthesis is challenging, making a rational search desirable. Here, we explored LaF3-LaX3 (X = Cl, Br, I) system using ab initio structure searches based on evolutionary algorithms, and predicted LaF2X and LaFX2 (X = Br, I), which are respectively isostructural with LaHBr2 and YH2I, consisting of layered La-F blocks with single and double ordered honeycomb lattices, separated by van der Waals gaps. We successfully synthesized these compounds: LaF2Br and LaFI2 crystallized in the predicted structure, while LaF2I is similar to the predicted one but with different layer stacking. LaF2I exhibits fluoride ion conductivity comparable to that of non-doped LaF3, and has the potential to show better ionic conductivity upon appropriate doping, given the theoretically lower diffusion energy barrier and the presence of soft iodine anions. This study shows the structure prediction using evolutionary algorithms will accelerate the discovery of mixed-anion compounds in future, in particular those with an ordered anion arrangement.

Evolutionary Algorithm Directed Synthesis of Mixed Anion Compounds LaF2X (X=Br, I) and LaFI2

AbstractMixed‐anion compounds have attracted growing attentions, but their synthesis is challenging, making a rational search desirable. Here, we explored LaF3‐LaX3 (X=Cl, Br, I) system using ab initio structure searches based on evolutionary algorithms, and predicted LaF2X and LaFX2 (X=Br, I), which are respectively isostructural with LaHBr2 and YH2I, consisting of layered La‐F blocks with single and double ordered honeycomb lattices, separated by van der Waals gaps. We successfully synthesized these compounds: LaF2Br and LaFI2 crystallize in the predicted structure, while LaF2I is similar to the predicted one but with different layer stacking. LaF2I exhibits fluoride ion conductivity comparable to that of non‐doped LaF3, and has the potential to show better ionic conductivity upon appropriate doping, given the theoretically lower diffusion energy barrier and the presence of soft iodine anions. This study shows the structure prediction using evolutionary algorithms will accelerate the discovery of mixed‐anion compounds in future, in particular those with an ordered anion arrangement.

Fluorosulfide La2+xSr1–xF4+xS2 with a Triple-Fluorite Layer Enabling Interstitial Fluoride-Ion Conduction

Fluoride-ion conducting solid materials are applicable as solid electrolytes for sensing devices and next-generation rechargeable batteries. Most of the previously reported materials have been limited to the single-anion compounds such as fluorite-type, tysonite-type, and perovskite-type structures. These suffered from further improvements by crystal structure modification which derives a paradigm shift in the material tailoring. Fluoride and sulfide ions prefer respective coordination environments because of the different ionic radii and electronegativity. This feature implies that fluorosulfide mixed-anion compounds have potential to form anion-ordering crystal structures with new fluoride-ion conducting layers. Herein, we have found that the fluorosulfide La2+xSr1–xF4+xS2 exhibits fluoride-ion conduction. The presence of multiple anions results in the formation of an anion-ordering two-dimensional crystal lattice with triple fluorite layers, which cannot be realized for metal fluorides. Sulfide ions in the crystal structure increase the number of interstitial sites of fluoride ions, forming a fluoride-ion conduction pathway.

Molten Salts-Driven Discovery of a Polar Mixed-Anion 3D framework at the nanoscale: Zn4Si2O7Cl2, Charge Transport and Photoelectrocatalytic Water Splitting.

Mixed-anion compounds widen the chemical space of attainable materials compared to single anionic compounds, but the exploration of their structural diversity is limited by common synthetic paths. Especially, oxychlorides rely mainly on layered structures, which suffer from low stability during photo(electro)catalytic processes. Herein we report a strategy to design a new polar 3D tetrahedral framework with composition Zn4Si2O7Cl2. We use a molten salt medium to enable low temperature crystallization of nanowires of this new compound, by relying on tetrahedral building units present in the melt to build the connectivity of the oxychloride. These units are combined with silicon-based connectors from a non-oxidic Zintl phase to enable precise tuning of the oxygen content. This structure brings high chemical and thermal stability, as well as strongly anisotropic hole mobility along the polar axis. These features, associated with the ability to adjust the transport properties by doping, enable to tune water splitting properties for photoelectrocatalytic H2 evolution and water oxidation. This work then paves the way to a new family of mixed-anion solids.

Synthesis of uranium mixed anion compounds synthesized using the Boron-Chalcogen Mixture method: Ba6Co6U0·91S13·5O0.5 and Ba5·47K0·53Zn6US13·5O0.5

Mixed anion compounds have exhibited interesting structures and properties that differ from compounds only incorporating a single anion in their composition. Unfortunately, difficulties in the synthetic methods used to obtain these materials has slowed the evolution of this field, prompting investigations into alternate synthetic pathways to these materials. Our recently establish Boron-Chalcogen Mixture (BCM) method, which was originally developed for the synthesis of pure actinide chalcogenides from oxides, has been adapted to achieve the partial oxide to sulfide conversion of Ba2MUO6 (M = Co, Zn) which resulted in two new uranium (IV/V) oxysulfide compounds, Ba6Co6U0·91S13·5O0.5 and Ba5·47K0·53Zn6US13·5O0.5 These compounds crystallize in the tetragonal crystal system adopting the space group I4/mcm. Their syntheses, crystal structures, and trends observed in the pursuit of these new mixed anion compounds are reported.

A Heteroanionic Zinc Ion Conductor for Dendrite-Free Zn Metal Anodes.

Although zinc-based batteries are promising candidates for eco-friendly and cost-effective energy storage devices, their performance is severely retarded by dendrite formation. As the simplest zinc compounds, zinc chalcogenides, and halides are individually applied as a Zn protection layer due to high zinc ion conductivity. However, the mixed-anion compounds are not studied, which constrains the Zn2+ diffusion in single-anion lattices to their own limits. A heteroanionic zinc ion conductor (Zny O1- x Fx ) coating layer is designed by in situ growth method with tunable F content and thickness. Strengthened by F aliovalent doping, the Zn2+ conductivity is enhanced within the wurtzite motif for rapid lattice Zn migration. Zny O1- x Fx also affords zincophilic sites for oriented superficial Zn plating to suppress dendrite growth. Therefore, Zny O1- x Fx -coated anode exhibits a low overpotential of 20.4mV for 1000h cycle life at a plating capacity of 1.0mAhcm-2 during symmetrical cell test. The MnO2 //Zn full battery further proves high stability of 169.7 mAhg-1 for 1000 cycles. This work may enlighten the mixed-anion tuning for high-performance Zn-based energy storage devices.

Ultralow thermal conductivity in the mixed-anion solid solution Sn2SbS2−xSexI3

The mixed-anion compounds Sn2SbS2−xSexI3 (x = 0, 0.2, 0.5) and Sn2BiS2I3 were synthesized and ultralow thermal conductiviy was found for the mixed-anion solid solution.