Effect of pre-intercalation on Li-ion diffusion mapped by topochemical single-crystal transformation and operando investigation.

Limitations in electrochemical performance as well as supply chain challenges have rendered positive electrode materials a critical bottleneck for Li-ion batteries. State-of-the-art Li-ion batteries fall short of accessing theoretical capacities. As such, there is intense interest in the design of strategies that enable the more effective utilization of active intercalation materials. Pre-intercalation with alkali-metal ions has attracted interest as a means of accessing higher reversible capacity and improved rate performance. However, the structural basis for improvements in electrochemical performance remains mostly unexplored. Here we use topochemical single-crystal-to-single-crystal transformations in a tunnel-structured ζ-V2O5 positive electrode to illustrate the effect of pre-intercalation in modifying the host lattice and altering diffusion pathways. Furthermore, operando synchrotron X-ray diffraction is used to map Li-ion site preferences and occupancies as a function of the depth of discharge in pre-intercalated materials. Na- and K-ion intercalation 'props open' the one-dimensional tunnel, reduces electrostatic repulsions between inserted Li ions and entirely modifies diffusion pathways, enabling orders of magnitude higher Li-ion diffusivities and accessing higher capacities. Deciphering the atomistic origins of improved performance in pre-intercalated materials on the basis of single-crystal-to-single-crystal topochemical transformation and operando diffraction studies paves the way to site-selective modification approaches for positive electrode design.

Improved Alcohol Oxidation through Combined Effects of Tensile Lattice Strain and Twin Defects in Core-Shell Electrocatalysts.

The direct alcohol fuel cells (DAFCs) rely on alcohol oxidation reactions (AORs) to produce electricity, which require catalysts with optimized electronic structure to accelerate the sluggish AORs. Herein, an epitaxial growth of Pd layer onto the pentatwinned Au@Ag core-shell nanorods (NRs) is reported to synthesize highly strained Au@AgPd core-shell NRs. The tensile strain in the AgPd shell of the Au@AgPd nanorods (NRs) arises not only from the core-shell lattice mismatch but also from twinning and lattice distortion occurring at the five twinned boundaries present in the structure. Theoretical simulations prove that the presence of tensile strains in the AgPd layer leads to a significant upward shift of the d-band center of the Pd site toward the Fermi level which remarkably changes the adsorption energy of alcohols on the surface. Highly strained Au@AgPd NRs show exceptional mass activities in electrochemical oxidation of biomass-derived alcohols (ethylene glycol, ethanol, and glycerol) reaching up to 18.66, 15.6, and 7.90 A mgpd -1 , respectively. These values are 23.3, 23.6, and 23.2 times higher than commercial Pd/C catalysts. This strain engineering strategy set the platform for the design and synthesis of highly efficient and versatile catalysts for the construction of high-performance DAFCs.

Catching an Oxo Vanadate Porous Acetylacetonate Covalent Adaptive Catalytic Network that Renders Mustard-Gas Simulant Harmless.

In this work, we illustrated the design and development of a metal-coordinated porous organic polymer (POP) namely VO@TPA-POP via a post-synthetic metalation strategy to incorporate oxo-vanadium sites in a pristine polymer (TPA-POP) having acetylacetonate (acac) as anchoring moiety. The as-synthesized VO@TPA-POP exhibited highly robust and porous framework, which has been utilized for thioanisole (TA) oxidation to its corresponding sulfoxide. The catalyst demonstrated notable stability and recyclability by maintaining its catalytic activity over multiple reaction cycles without any significant loss in activity. The X-ray absorption spectroscopy (XAS) and density functional theory (DFT) analysis establish the existence of V(+4) oxidation state along with the VO(O)4 active sites into the porous network and the most energetically feasible mechanistic pathway involved in the TA oxidation, respectively, indicating the role of electron density associated with vanadium center during the catalytic transformation. Thus, this work aims at the demonstration of versatility and potential of VO@TPA-POP as a porous heterogeneous catalyst for the TA oxidation followed by decontamination of sulfur mustards (HD's) to their corresponding less toxic sulfoxides in a more efficient and greener way.

Defects Tune the Strong Metal-Support Interactions in Copper Supported on Defected Titanium Dioxide Catalysts for CO2 Reduction.

A highly active and stable Cu-based catalyst for CO2 to CO conversion was demonstrated by creating a strong metal-support interaction (SMSI) between Cu active sites and the TiO2-coated dendritic fibrous nano-silica (DFNS/TiO2) support. The DFNS/TiO2-Cu10 catalyst showed excellent catalytic performance with a CO productivity of 5350 mmol g-1 h-1 (i.e., 53,506 mmol gCu-1 h-1), surpassing that of almost all copper-based thermal catalysts, with 99.8% selectivity toward CO. Even after 200 h of reaction, the catalyst remained active. Moderate initial agglomeration and high dispersion of nanoparticles (NPs) due to SMSI made the catalysts stable. Electron energy loss spectroscopy confirmed the strong interactions between copper NPs and the TiO2 surface, supported by in situ diffuse reflectance infrared Fourier transform spectroscopy and X-ray photoelectron spectroscopy. The H2-temperature programmed reduction (TPR) study showed α, ß, and γ H2-TPR signals, further confirming the presence of SMSI between Cu and TiO2. In situ Raman and UV-vis diffuse reflectance spectroscopy studies provided insights into the role of oxygen vacancies and Ti3+ centers, which were produced by hydrogen, then consumed by CO2, and then again regenerated by hydrogen. These continuous defect generation-regeneration processes during the progress of the reaction allowed long-term high catalytic activity and stability. The in situ studies and oxygen storage complete capacity indicated the key role of oxygen vacancies during catalysis. The in situ time-resolved Fourier transform infrared study provided an understanding of the formation of various reaction intermediates and their conversion to products with reaction time. Based on these observations, we have proposed a CO2 reduction mechanism, which follows a redox pathway assisted by hydrogen.

CsPbCl3 → CsPbI3 Exchange in Perovskite Nanocrystals Proceeds through a Jump-the-Gap Reaction Mechanism.

Halide exchange is a popular strategy to tune the properties of CsPbX3 nanocrystals after synthesis. However, while Cl → Br and Br → I exchanges proceed through the formation of stable mixed-halide nanocrystals, the Cl ⇌ I exchange is more elusive. Indeed, the large size difference between chloride and iodide ions causes a miscibility gap in the CsPbCl3-CsPbI3 system, preventing the isolation of stable CsPb(ClxI1-x)3 nanocrystals. Yet, previous works have claimed that a full CsPbCl3 → CsPbI3 exchange can be achieved. Even more interestingly, interrupting the exchange prematurely yields a mixture of CsPbCl3 and CsPbI3 nanocrystals that coexist without undergoing further transformation. Here, we investigate the reaction mechanism of CsPbCl3 → CsPbI3 exchange in nanocrystals. We show that the reaction proceeds through the early formation of iodide-doped CsPbCl3 nanocrystals covered by a monolayer shell of CsI. These nanocrystals then leap over the miscibility gap between CsPbCl3 and CsPbI3 by briefly transitioning to short-lived and nonrecoverable CsPb(ClxI1-x)3 nanocrystals, which quickly expel the excess chloride and turn into the chloride-doped CsPbI3 nanocrystals found in the final product.

Incorporation of Bimetallic Sulfide with Carbon Nitride for Advanced Na-Ion Batteries.

Sodium-ion batteries (SIBs) have received tremendous attention owing to their low cost, high working voltages, and energy density. However, the design and development of highly efficient SIBs represent a great challenge. Here, a unique and reliable approach is reported to prepare carbon nitride (CN) hybridized with nickel iron sulfide (NFCN) using simple reaction between Ni-Fe layered double hydroxide and dithiooxamide. The characterization results demonstrate that the hybridization with optimal amount of CN induces local distortion in the crystal structure of the hybrid, which would benefit SIB performance. Systematic electrochemical studies with a half-cell configuration show that the present hybrid structure exhibits a promising reversible specific capacity of 348 mAh g-1 at 0.1 A g-1 after 100 cycles with good rate capability. Simulation result reveals that the iron atoms in nickel iron sulfide act as a primary active site to accommodate Na+ ions. At last, with a full cell configuration using NFCN and Na3 V2 (PO4 )2 O2 F as the anode and cathode, respectively, the specific capacity appears to be ≈95 mAh g-1 after 50 cycles at 0.1 A g-1 condition. This excellent performance of these hybrids can be attributed to the synergistic effect of the incorporated CN species and the high conductivity of nickel-iron sulfide.

Zinc-Substituted Cobalt Phosphate [ZnCo2(PO4)2] as a Bifunctional Electrocatalyst.

Development of highly efficient, earth-abundant, and stable bifunctional electrocatalysts is pivotal for designing viable next-generation metal-air batteries. Cobalt-based phosphates provide a treasure house to design electrocatalysts, with a wide range of cation substitutions to further enhance their electrocatalytic activity. In particular, phosphates with distorted geometry show favorable binding efficiency toward water molecules with low overpotential. In the present work, zinc-substituted cobalt phosphate ZnCo2(PO4)2 was investigated. Its crystal structure was solved to a monoclinic framework built with CoO6 octahedra and distorted CoO5/ZnO5 trigonal bipyramid leading to efficient bifunctional electrocatalytic activity. It offers robust structural stability with onset potential values of 0.87 V (vs reversible hydrogen electrode (RHE)) and 1.50 V (vs RHE) for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) processes, respectively, comparable to the precious metal catalysts. The origin and stability of the bifunctional activity were probed by combining ex situ diffraction and electron microscopy corroborated by ab initio calculations. Overall, zinc-substituted cobalt phosphate [ZnCo2(PO4)2] forms a potential bifunctional electrocatalyst with tunable local cobalt coordination that can be harnessed for metal-air batteries.

Tuning the Electronic Structure of a Ni-Vacancy-Enriched AuNi Spherical Nanoalloy via Electrochemical Etching for Water Oxidation Studies in Alkaline and Neutral Media.

Internal Ni-vacancy-enriched spherical AuNi nanoalloys (AuNi1-2-T) have been prepared via a noble electrochemical etching method. AuNi1.5-T showed the highest oxygen evolution reaction (OER) activity compared to bare AuNi1.5, and it demands only 239 mV overpotential, which was 134 mV lesser than the overpotential required by commercial RuO2 at 10 mA cm-2 current density in a 1 M KOH solution (pH = 14). The calculated turnover frequency (TOF) value for AuNi1.5-T (0.0229 s-1) was 11.74 times higher than that of AuNi1.5 (0.00195 s-1). Also, the electrochemically activated AuNi1.5-T showed superior neutral water oxidation activity by demanding only 335 mV overpotential with a TOF value of 0.000135 s-1 in a 1 M Na2SO4 solution (pH = 7) at 10 mA cm-2. The long-term stability studies (over 60 h) reveal the excellent robustness of an electrochemically treated alloy system. Density functional theory based electronic structure calculations showed that in the case of AuNi and AuNi1.5, Au d, Au s, and Ni d orbitals have significant contributions, whereas in the Ni-vacant systems, the density of states is mainly governed by d orbitals of Au and Ni. Also, the Ni-vacant system possesses a work function value of 4.96 eV, which is lower than that of the pristine system (5.27 eV) and thereby favored OH- binding with an optimum adsorption energy. This result is in reasonable agreement with the experimental outcome of an accelerated OER in a vacancy-enriched Ni-rich AuNi alloy system. Also, mechanistic analysis reveals that the creation of a Ni vacancy can effectively alter the overall mechanism of the OER and thereby facilitate the same with a lower applied energy.

Progress and challenges in layered two-dimensional hybrid perovskites.

Dimensionality is the game-changer property of a material. The optical and electronic properties of a compound get dramatically influenced by confining dimensions from 3D to 2D. The bulk 3D perovskite materials have shown remarkable up-gradation in the power conversion efficiency, hence grabbing worldwide attention. But instability against moisture, temperature, and ion migration are the factors constantly back-stabbing and hindering from full-scale commercialization. 2D perovskite material has emerged as an excellent bridging entity between structural-chemical stability, and viable commercialization. Organic-inorganic 2D perovskite materials come with a layered structure in which a large organic cation layer as a spacer is sandwiched between two inorganic metal halide octahedra layers. Moreover, hydrophobic spacer cations are employed which isolate inorganic octahedral layers from water molecules. Hydrophobic spacer cations protect the authentic structure from being degraded. These layered structures occur in two phases namely the Ruddlesden-Popper phase and Dion-Jacobson phase, depending on the spacer cation types. Alternating inorganic and organic layers form multiple quantum wells naturally, along with spin-orbit-coupling gives Rashba splitting. 2D perovskite materials are coming up with interesting chemical, physical properties like exciton dynamics, charge carrier transport, and electron-phonon coupling as a result of the quantum confinement effect. Despite appreciable stability, limited charge transport and large bandgap are limiting the application of 2D perovskite materials in solar cells. These limitations can be overcome by using the concept of 2D/3D multidimensional hybrid perovskites, which includes the long-term stability of 2D perovskite and the high performance of 3D perovskite at the same time. Here in this perspective, we have given brief insight on structural versatility, synthesis techniques, some of the unique photophysical properties, potential device fabrication, and recent advancements in the 2D structure to stand against degradation. Certain shortcomings and future outlooks are also discussed to make the perspective more informative.

Wheat grain proteomic and protein-metabolite interactions analyses provide insights into plant growth promoting bacteria-arbuscular mycorrhizal fungi-wheat interactions.

KEY MESSAGE: Proteomic, protein-protein and protein-metabolite interaction analyses in wheat inoculated with PGPB and AMF identified key proteins and metabolites that may have a role in enhancing yield and biofortification. Plant growth-promoting bacteria (PGPB) and arbuscular mycorrhizal fungi (AMF) have an impact on grain yield and nutrition. This dynamic yet complex interaction implies a broad reprogramming of the plant's metabolic and proteomic activities. However, little information is available regarding the role of native PGPB and AMF and how they affect the plant proteome, especially under field conditions. Here, proteomic, protein-protein and protein-metabolite interaction studies in wheat triggered by PGPB, Bacillus subtilis CP4 either alone or together with AMF under field conditions was carried out. The dual inoculation with native PGPB (CP4) and AMF promoted the differential abundance of many proteins, such as histones, glutenin, avenin and ATP synthase compared to the control and single inoculation. Interaction study of these differentially expressed proteins using STRING revealed that they interact with other proteins involved in seed development and abiotic stress tolerance. Furthermore, these interacting proteins are involved in carbon fixation, sugar metabolism and biosynthesis of amino acids. Molecular docking predicted that wheat seed storage proteins, avenin and glutenin interact with secondary metabolites, such as trehalose, and sugars, such as xylitol. Mapping of differentially expressed proteins to KEGG pathways showed their involvement in sugar metabolism, biosynthesis of secondary metabolites and modulation of histones. These proteins and metabolites can serve as markers for improving wheat-PGPB-AMF interactions leading to higher yield and biofortification.

Advanced descriptors for long-range noncovalent interactions between SARS-CoV-2 spikes and polymer surfaces.

The recent pandemic triggered numerous societal efforts aimed to control and limit the spread of SARS-CoV-2. One of these aspects is related on how the virion interacts with inanimate surfaces, which might be the source of secondary infection. Although recent works address the adsorption of the spike protein on surfaces, there is no information concerning the long-range interactions between spike and surfaces, experimented by the virion when is dispersed in the droplet before its possible adsorption. Some descriptors, namely the interaction potentials per single protein and global potentials, were calculated in this work. These descriptors, evaluated for the closed and open states of the spike protein, are correlated to the long-range noncovalent interactions between the SARS-CoV-2 spikes and polymeric surfaces. They are associated with the surface's affinity towards SARS-CoV-2 dispersed in respiratory droplets or water solutions. Molecular-Dynamics simulations were performed to model the surface of three synthetic polymeric materials: Polypropylene (PP), Polyethylene Terephthalate (PET), and Polylactic Acid (PLA), used in Molecular Mechanics simulations to define the above potentials. The descriptors show a similar trend for the three surfaces, highlighting a greater affinity towards the spikes of PP and PLA over PET. For closed and open structures, the long-range interactions with the surfaces decreased in the following order PP âˆ¼ PLA > PET and PLA > PP > PET, respectively. Thus, PLA and PP interact with the virion quite distant from these surfaces to a greater extent concerning the PET surface, however, the differences among the considered surfaces were small. The global potentials show that the long-range interactions are weak compared to classic binding energy of covalent or ionic bonds. The proposed descriptors are useful most of all for a comparative study aimed at quickly preliminary screening of polymeric surfaces. The obtained results should be validated by more accurate method which will be subject of a subsequent work.

Finding the catalytically active sites on the layered tri-chalcogenide compounds CoPS3 and NiPS3 for hydrogen evolution reaction.

Electronic structure calculations based on density functional theory are used to identify the catalytically active sites for the hydrogen evolution reaction on single layers of the two transition metal tri-chalcogenide compounds CoPS3 and NiPS3. Some of the under-coordinated P and S atoms at the edges are found to act as the active sites, the details of which depend on the coverage of H on the electrode. Overpotentials along the two possible pathways for HER are also estimated for the two materials. These findings not only resolve an apparent discrepancy between published experimental results and our earlier calculations, but also provide insights which can be used to enhance catalytic efficiency of these materials further.

Halide Replacement with Complete Preservation of Crystal Lattice in Mixed-Anion Lanthanide Oxyhalides.

A challenge in anion control in periodic solids is to preserve the crystal lattice while substituting for different anions of widely varying size and hardness. Post-synthetic modification routes that place cations or anions in non-equilibrium configurations are promising; however, such methods remain relatively unexplored for anion placement. Here, we report the synthesis of LaOI nanocrystals by a non-hydrolytic sol-gel condensation reaction and their transformation into LaOBr, LaOCl, and LaOF nanocrystals along hard-soft acid-base principles using post-synthetic metathesis reactions with ammonium halides. Anion displacement proceeds along halide planes, preserving the tetragonal matlockite structure. Energy-variant X-ray excited optical luminesce signatures of alloyed Tb3+ -ions is a sensitive quantum reporter of the preservation of the cation sublattice and hardening of the crystal structure upon anion replacement.

An Organic-Inorganic Perovskitoid with Zwitterion Cysteamine Linker and its Crystal-Crystal Transformation to Ruddlesden-Popper Phase.

We demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous.

Rainforest-initiated wet season onset over the southern Amazon.

Although it is well established that transpiration contributes much of the water for rainfall over Amazonia, it remains unclear whether transpiration helps to drive or merely responds to the seasonal cycle of rainfall. Here, we use multiple independent satellite datasets to show that rainforest transpiration enables an increase of shallow convection that moistens and destabilizes the atmosphere during the initial stages of the dry-to-wet season transition. This shallow convection moisture pump (SCMP) preconditions the atmosphere at the regional scale for a rapid increase in rain-bearing deep convection, which in turn drives moisture convergence and wet season onset 2-3 mo before the arrival of the Intertropical Convergence Zone (ITCZ). Aerosols produced by late dry season biomass burning may alter the efficiency of the SCMP. Our results highlight the mechanisms by which interactions among land surface processes, atmospheric convection, and biomass burning may alter the timing of wet season onset and provide a mechanistic framework for understanding how deforestation extends the dry season and enhances regional vulnerability to drought.

A New Era of Antibiotics: The Clinical Potential of Antimicrobial Peptides.

Antimicrobial resistance is a multifaceted crisis, imposing a serious threat to global health. The traditional antibiotic pipeline has been exhausted, prompting research into alternate antimicrobial strategies. Inspired by nature, antimicrobial peptides are rapidly gaining attention for their clinical potential as they present distinct advantages over traditional antibiotics. Antimicrobial peptides are found in all forms of life and demonstrate a pivotal role in the innate immune system. Many antimicrobial peptides are evolutionarily conserved, with limited propensity for resistance. Additionally, chemical modifications to the peptide backbone can be used to improve biological activity and stability and reduce toxicity. This review details the therapeutic potential of peptide-based antimicrobials, as well as the challenges needed to overcome in order for clinical translation. We explore the proposed mechanisms of activity, design of synthetic biomimics, and how this novel class of antimicrobial compound may address the need for effective antibiotics. Finally, we discuss commercially available peptide-based antimicrobials and antimicrobial peptides in clinical trials.

Bi3+ -Er3+ and Bi3+ -Yb3+ Codoped Cs2 AgInCl6 Double Perovskite Near-Infrared Emitters.

Bi3+ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi3+ and lanthanide ions. Codoping of Bi3+ and Ln3+ (Ln=Er and Yb) in Cs2 AgInCl6 double perovskite is presented. Bi3+ -Er3+ codoped Cs2 AgInCl6 shows Er3+ f-electron emission at 1540 nm (suitable for low-loss optical communication). Bi3+ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi3+ -Er3+ codoped Cs2 AgInCl6 shows ca. 45 times higher emission intensity compared to the Er3+ doped Cs2 AgInCl6 . Similar results are also observed in Bi3+ -Yb3+ codoped sample emitting at 994 nm. A combination of temperature-dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.

Tweaking Nickel with Minimal Silver in a Heterogeneous Alloy of Decahedral Geometry to Deliver Platinum-like Hydrogen Evolution Activity.

Five-fold intertwined Agx Ni1-x (x=0.01-0.25) heterogeneous alloy nanocrystal (NC) catalysts, prepared through unique reagent combinations, are presented. With only ca. 5 at % Ag (AgNi-5), Pt-like activity has been achieved at pH 14. To reach a current density of 10 mA cm-2 the extremely stable AgNi-5 requires an overpotential of 24.0±1.2 mV as compared to 20.1±0.8 mV for 20 % Pt/C, both with equal catalyst loading of 1.32 mg cm-2 . The turnover frequency (TOF) is as high as 2.1 H2  s-1 at 50 mV (vs. RHE). Site-specific elemental analyses show the Ag:Ni compositional variation, where the apex and edges of the decahedra are Ag-rich, thereby exposing Ni onto the faces to achieve maximum charge transport for an exceptional pH universal HER activity. DFT calculations elucidate the relative H-atom adsorption capability of the Ni centers as a function of their proximity to Ag atom.

TiS2 Monolayer as an Emerging Ultrathin Bifunctional Catalyst: Influence of Defects and Functionalization.

We have envisaged the hydrogen evolution and oxygen evolution reactions (HER and OER) on a two-dimensional (2D) noble-metal-free titanium disulfide (TiS2 ) monolayer, which belongs to the exciting family of transition metal dichalcogenides (TMDCs). Our theoretical investigation to probe the HER and OER on both the H and T phases of 2D TiS2 is based on electronic-structure calculations witihin the framework of density functional theory (DFT). Since TiS2 is the lightest compound among the group-IV TMDCs, it is worth exploring the catalytic activity of a TiS2 monolayer through the functionalization at the anion (S) site, substituting with P, N, and C dopants as well as by incorporating single sulfur vacancy defects. We have investigated the effect of functionalization and vacancy defects on the structural, electronic, and optical response of a TiS2 monolayer by determining the density of states, work-function, and optical absorption spectra. We have determined the HER and OER activities for the functionalized and defective TiS2 monolayers based on the reaction coordinate, which can be constructed from the adsorption free energies of the intermediates (H*, O*, OH* and OOH*, where * denotes the adosrbed state) in the HER and OER mechanisms. Finally, we have shown that TiS2 monolayers are emerging as a promising material for the HER and OER mechanisms under the influence of functionalization and defects.

Cesium Bismuth Iodide Solar Cells from Systematic Molar Ratio Variation of CsI and BiI3.

Metal halide compounds with photovoltaic properties prepared from solution have received increased attention for utilization in solar cells. In this work, low-toxicity cesium bismuth iodides are synthesized from solution, and their photovoltaic and optical properties as well as electronic and crystal structures are investigated. The X-ray diffraction patterns reveal that a CsI/BiI3 precursor ratio of 1.5:1 can convert pure rhombohedral BiI3 to pure hexagonal Cs3Bi2I9, but any ratio intermediate of this stoichiometry and pure BiI3 yields a mixture containing the two crystalline phases Cs3Bi2I9 and BiI3, with their relative fraction depending on the CsI/BiI3 ratio. Solar cells from the series of compounds are characterized, showing the highest efficiency for the compounds with a mixture of the two structures. The energies of the valence band edge were estimated using hard and soft X-ray photoelectron spectroscopy for more bulk and surface electronic properties, respectively. On the basis of these measurements, together with UV-vis-near-IR spectrophotometry, measuring the band gap, and Kelvin probe measurements for estimating the work function, an approximate energy diagram has been compiled clarifying the relationship between the positions of the valence and conduction band edges and the Fermi level.