Structure and dynamics of Li1.24K0.76CO3 molten carbonate electrolyte from molecular simulations with explicit polarization.

Molten carbonate electrolysis cells represent a key technology for harnessing surplus energy from renewable sources and converting it into gaseous energy carriers. To optimize their efficiency, a comprehensive understanding of each step in the operational process is essential. Here, we focus on the electrolyte of choice in molten carbonate cells: the Li1.24K0.76CO3 melt. Utilizing molecular dynamics with explicit polarization, we demonstrate that the structure of this molten mixture is characterized by a dense network of lithium-carbonate complexes, with K+ ions loosely embedded within this network. This structural insight enables us to rationalize from an atomistic perspective the conductivity trends observed experimentally in molten carbonates. Moreover, our work highlights the importance of including polarization for the simulations of dense liquid carbonates. It also acts as a foundational step towards more advanced theoretical studies for elucidating the role of the electrolyte in these devices.

Exploring zinc oxide morphologies for aqueous solar cells by a photoelectrochemical, computational, and multivariate approach.

Dye-sensitized solar cells assembled with aqueous electrolytes are emerging as a sustainable photovoltaic technology suitable for safe indoor and portable electronics use. While the scientific community is exploring unconventional materials for preparing electrodes and electrolytes, this work presents the first study on zinc oxide as a semiconductor material to fabricate photoanodes for aqueous solar cells. Different morphologies (i.e., nanoparticles, multipods, and desert roses) are synthesized, characterized, and tested in laboratory-scale prototypes. This exploratory work, also integrated by a computational study and a multivariate investigation on the factors that influence electrode sensitization, confirms the possibility of using zinc oxide in the field of aqueous photovoltaics and opens the way to new morphologies and processes of functionalization or surface activation to boost the overall cell efficiency.

Halide Engineering in Mixed Halide Perovskite-Inspired Cu2AgBiI6 for Solar Cells with Enhanced Performance.

Cu2AgBiI6 (CABI) is a promising perovskite-inspired absorber for solar cells due to its direct band gap and high absorption coefficient. However, the nonradiative recombination caused by the high extrinsic trap density limits the performance of CABI-based solar cells. In this work, we employ halide engineering by doping bromide anions (Br-) in CABI thin films, in turn significantly improving the power conversion efficiency (PCE). By introducing Br- in the synthetic route of CABI thin films, we identify the optimum composition as CABI-10Br (with 10% Br at the halide site). The tailored composition appears to reduce the deep trap density as shown by time-resolved photoluminescence and transient absorption spectroscopy characterizations. This leads to a dramatic increase in the lifetime of charge carriers, which therefore improves both the external quantum efficiency and the integrated short-circuit current. The photovoltaic performance shows a significant boost since the PCE under standard 1 sun illumination increases from 1.32 to 1.69% (∼30% relative enhancement). Systematic theoretical and experimental characterizations were employed to investigate the effect of Br- incorporation on the optoelectronic properties of CABI. Our results highlight the importance of mitigating trap states in lead-free perovskite-inspired materials and that Br- incorporation at the halide site is an effective strategy for improving the device performance.

Exotic hexagonal NaCl atom-thin layer on methylammonium lead iodide perovskite: new hints for perovskite solar cells from first-principles calculations.

Alkali halides are simple inorganic compounds extensively used as surface modifiers in optoelectronic devices. In perovskite solar cells (PSCs), they act as interlayers between the light absorber material and the charge selective layers improving their contact quality. They introduce surface dipoles that enable the fine tuning of the relative band alignment and passivate surface defects, a well-known drawback of hybrid organic-inorganic perovskites, that is responsible for most of the issues hampering the long-term performances. Reducing the thickness of such salt-based insulating layer might be beneficial in terms of charge transfer between the perovskite and the electron/hole transport layers. In this context, here we apply density functional theory (DFT) to characterize the structure and the electronic features of atom-thin layers of NaCl adsorbed on the methylammonium lead iodide (MAPI) perovskite. We analyze two different models of MAPI surface terminations and find unexpected structural reconstructions arising at the interface. Unexpectedly, we find an exotic honeycomb-like structuring of the salt, also recently observed in experiments on a diamond substrate. We also investigate how the salt affects the perovskite electronic properties that are key to control the charge dynamics at the interface. Moreover, we also assess the salt ability to improve the defect tolerance of the perovskite surface. With these results, we derive new hints regarding the potential benefits of using an atom-thin layer of alkali halides in PSCs.

Azobenzene-based optoelectronic transistors for neurohybrid building blocks.

Exploiting the light-matter interplay to realize advanced light responsive multimodal platforms is an emerging strategy to engineer bioinspired systems such as optoelectronic synaptic devices. However, existing neuroinspired optoelectronic devices rely on complex processing of hybrid materials which often do not exhibit the required features for biological interfacing such as biocompatibility and low Young's modulus. Recently, organic photoelectrochemical transistors (OPECTs) have paved the way towards multimodal devices that can better couple to biological systems benefiting from the characteristics of conjugated polymers. Neurohybrid OPECTs can be designed to optimally interface neuronal systems while resembling typical plasticity-driven processes to create more sophisticated integrated architectures between neuron and neuromorphic ends. Here, an innovative photo-switchable PEDOT:PSS was synthesized and successfully integrated into an OPECT. The OPECT device uses an azobenzene-based organic neuro-hybrid building block to mimic the retina's structure exhibiting the capability to emulate visual pathways. Moreover, dually operating the device with opto- and electrical functions, a light-dependent conditioning and extinction processes were achieved faithful mimicking synaptic neural functions such as short- and long-term plasticity.

Structural Evolution of Air-Exposed Layered Oxide Cathodes for Sodium-Ion Batteries: An Example of Ni-doped NaxMnO2.

Sodium-ion batteries have recently aroused the interest of industries as possible replacements for lithium-ion batteries in some areas. With their high theoretical capacities and competitive prices, P2-type layered oxides (NaxTMO2) are among the obvious choices in terms of cathode materials. On the other hand, many of these materials are unstable in air due to their reactivity toward water and carbon dioxide. Here, Na0.67Mn0.9Ni0.1O2 (NMNO), one of such materials, has been synthesized by a classic sol-gel method and then exposed to air for several weeks as a way to allow a simple and reproducible transition toward a Na-rich birnessite phase. The transition between the anhydrous P2 to the hydrated birnessite structure has been followed via periodic XRD analyses, as well as neutron diffraction ones. Extensive electrochemical characterizations of both pristine NMNO and the air-exposed one vs sodium in organic medium showed comparable performances, with capacities fading from 140 to 60 mAh g-1 in around 100 cycles. Structural evolution of the air-exposed NMNO has been investigated both with ex situ synchrotron XRD and Raman. Finally, DFT analyses showed similar charge compensation mechanisms between P2 and birnessite phases, providing a reason for the similarities between the electrochemical properties of both materials.

Interface Modification for Energy Level Alignment and Charge Extraction in CsPbI3 Perovskite Solar Cells.

In perovskite solar cells (PSCs) energy level alignment and charge extraction at the interfaces are the essential factors directly affecting the device performance. In this work, we present a modified interface between all-inorganic CsPbI3 perovskite and its hole-selective contact (spiro-OMeTAD), realized by the dipole molecule trioctylphosphine oxide (TOPO), to align the energy levels. On a passivated perovskite film, with n-octylammonium iodide (OAI), we created an upward surface band-bending at the interface by TOPO treatment. This improved interface by the dipole molecule induces a better energy level alignment and enhances the charge extraction of holes from the perovskite layer to the hole transport material. Consequently, a Voc of 1.2 V and a high-power conversion efficiency (PCE) of over 19% were achieved for inorganic CsPbI3 perovskite solar cells. Further, to demonstrate the effect of the TOPO dipole molecule, we present a layer-by-layer charge extraction study by a transient surface photovoltage (trSPV) technique accomplished by a charge transport simulation.

First-principles design of nanostructured electrode materials for Na-ion batteries: challenges and perspectives.

Post-lithium batteries are emerging as viable solutions for sustainable energy transition. Effective deployment in the market calls for great research efforts in the identification of novel component materials and the assessment of related working principles. Computational modelling can be a key player in boosting innovation and development by enabling rational strategies for the design of appropriately tuned materials with optimized activity towards battery operating processes. By gaining access to the structural and electronic features of functional electrodes, state-of-the-art DFT methods can unveil the subtle structure-property relationship that affects the uptake, transport, and storage efficiency. Hereby, we aim at reviewing the research status of theoretical advances in the field of Na-ion batteries (NIBs) and illustrating to what extent atomistic insights into sodiation/desodiation mechanisms of nanostructured materials can assist the development of effective anodes and cathodes for stable and highly performing devices. Thanks to increasing computer power and fruitful cooperation between theory and experiments, the route for effective design methodologies is being paved and will feed the upcoming developments in NIB technology.

New Insights on Singlet Oxygen Release from Li-Air Battery Cathode: Periodic DFT Versus CASPT2 Embedded Cluster Calculations.

Li-air batteries are a promising energy storage technology for large-scale applications, but the release of highly reactive singlet oxygen (1O2) during battery operation represents a main concern that sensibly limits their effective deployment. An in-depth understanding of the reaction mechanisms underlying the 1O2 formation is crucial to prevent its detrimental reactions with the electrolyte species. However, describing the elusive chemistry of highly correlated species such as singlet oxygen represents a challenging task for state-of-the-art theoretical tools based on density functional theory. Thus, in this study, we apply an embedded cluster approach, based on CASPT2 and effective point charges, to address the evolution of 1O2 at the Li2O2 surface during oxidation, i.e., the battery charging process. Based on recent hypothesis, we depict a feasible O22-/O2-/O2 mechanisms occurring from the (112̅0)-Li2O2 surface termination. Our highly accurate calculations allow for the identification of a stable superoxide as local minimum along the potential energy surface (PES) for 1O2 release, which is not detected by periodic DFT. We find that 1O2 release proceeds via a superoxide intermediate in a two-step one-electron process or another still accessible pathway featuring a one-step two-electron mechanism. In both cases, it represents a feasible product of Li2O2 oxidation upon battery charging. Thus, tuning the relative stability of the intermediate superoxide species can enable key strategies aiming at controlling the detrimental development of 1O2 for new and highly performing Li-air batteries.

Antimony-Bismuth Alloying: The Key to a Major Boost in the Efficiency of Lead-Free Perovskite-Inspired Photovoltaics.

The perovskite-inspired Cu2 AgBiI6 (CABI) material has been gaining increasing momentum as photovoltaic (PV) absorber due to its low toxicity, intrinsic air stability, direct bandgap, and a high absorption coefficient in the range of 105  cm-1 . However, the power conversion efficiency (PCE) of existing CABI-based PVs is still seriously constrained by the presence of both intrinsic and surface defects. Herein, antimony (III) (Sb3+ ) is introduced into the octahedral lattice sites of the CABI structure, leading to CABI-Sb with larger crystalline domains than CABI. The alloying of Sb3+ with bismuth (III) (Bi3+ ) induces changes in the local structural symmetry that dramatically increase the formation energy of intrinsic defects. Light-intensity dependence and electron impedance spectroscopic studies show reduced trap-assisted recombination in the CABI-Sb PV devices. CABI-Sb solar cells feature a nearly 40% PCE enhancement (from 1.31% to 1.82%) with respect to the CABI devices mainly due to improvement in short-circuit current density. This work will promote future compositional design studies to enhance the intrinsic defect tolerance of next-generation wide-bandgap absorbers for high-performance and stable PVs.

First-principles study of interfacial features and charge dynamics between spiro-MeOTAD and photoactive lead halide perovskites.

The main stability and performance issues of perovskite solar cells arise from the interfaces between the perovskite and the hole transport material. Here we address these interface issues by means of state-of-the-art first-principles calculations, providing new insights into charge transfer times and mechanisms and how they depend on the perovskite chemical composition and local interfacial environment.

Conductivity in Thin Films of Transition Metal Coordination Complexes.

Two coordination complexes have been made by combining the dithiolene complexes [M(mnt)2]2- (mnt = maleonitriledithiolate; M = Ni2+ or Cu2+) as anion, with the copper(II) coordination complex [Cu(Stetra)] (Stetra = 6,6'-bis(4,5-dihydrothiazol-2-yl)-2,2'-bipyri-dine) as cation. The variation of the metal centers leads to a dramatic change in the conductivity of the materials, with the M = Cu2+ variant (Cu-Cu) displaying semiconductor behavior with a conductivity of approximately 2.5 × 10-8 S cm-1, while the M = Ni2+ variant (Ni-Cu) displayed no observable conductivity. Computational studies found Cu-Cu enables a minimization of reorganization energy losses and, as a result, a lower barrier to the charge transfer process, resulting in the reported higher conductivity.

First-Principles Study of Cu-Based Inorganic Hole Transport Materials for Solar Cell Applications.

Perovskite solar cells (PSCs) and dye-sensitized solar cells (DSCs) both represent promising strategies for the sustainable conversion of sunlight into electricity and fuels. However, a few flaws of current devices hinder the large-scale establishment of such technologies. On one hand, PSCs suffer from instabilities and undesired phenomena mostly linked to the perovskite/hole transport layer (HTL) interface. Most of the currently employed organic HTL (e.g., Spiro-OMeTAD) are supposed to contribute to the perovskite decomposition and to be responsible for charge recombination processes and polarization barriers. On the other hand, power conversion efficiencies (PCEs) of DSCs are still too low to compete with other conversion technologies. Tandem cells are built by assembling p-type and n-type DSCs in a cascade architecture and, since each dye absorbs on a different portion of the solar spectrum, the harvesting window is increased and the theoretical efficiency limit for a single chromophore (i.e., the Shockley-Queisser limit) is overcome. However, such a strategy is hindered by the lack of a p-type semiconductor with optimal photocathode features. Nickel oxide has been, by far, the first-choice inorganic p-type semiconductor for both PV technologies, but its toxicity and non-optimal features (e.g., too low open circuit voltage and the presence of trap states) call for alternatives. Herein, we study of three p-type semiconductors as possible alternative to NiO, namely CuI, CuSCN and Cu2O. To this aim, we compare the structural and electronic features of the three materials by means of a unified theoretical approach based on the state-of-the art density functional theory (DFT). We focus on the calculation of their valence band edge energies and compare such values with those of two widely employed photo-absorbers, i.e., methylammonium lead iodide (MAPI) and the triple cation MAFACsPbBrI in PSCs and P1 and Y123 dyes in DSCs, given that the band alignment and the energy offset are crucial for the charge transport at the interfaces and have direct implications on the final efficiency. We dissect the effect a copper vacancy (i.e., intrinsic p-type doping) on the alignment pattern and rationalize it from both a structural and an electronic perspective. Our data show how defects can represent a crucial degree of freedom to control the driving force for hole injection in these devices.

Electronic structure and interfacial features of triphenylamine- and phenothiazine-based hole transport materials for methylammonium lead iodide perovskite solar cells.

Recently, great research efforts have been devoted to perovskite solar cells (PSCs) leading to sunlight-to-power conversion efficiencies above 25%. However, several barriers still hinder the full deployment of these devices. Critical issues are related to PCE stability and device lifetimes, which could be improved by targeted engineering of the hole transport material (HTM). Indeed, the HTM is not only responsible for transporting holes and preventing direct contact between the photo-active perovskite and the charge collector layer, but it plays important structural and protective roles too. As alternatives to the widely used yet expensive and unstable Spiro-OMeTAD, organic HTMs based on triphenylamine (TPA) and phenothiazine (PTZ) moieties have been proposed. However, their performances in PSC devices, and in particular their interfacial properties with the most popular methylammonium lead iodide perovskite (MAPI) still need investigations to be fully determined. In this framework, here we report a first-principles study on the structural and the electronic properties of a recently designed TPA and PTZ-based HTM (HTM1) and its interface with the MAPI (001) surface, considering both the PbI2- and the MAI-terminations. We also addressed already known HTM molecular systems to allow for a direct comparison with the recently proposed HTM1: we characterized the molecular parameters and the MAPI/HTM interfacial properties for Spiro-OMeTAD, PTZ1, and PTZ2. Our results suggest that good adhesion properties do not ensure effective and efficient MAPI-HTM hole injection. Despite the theoretical good alignment between HTM1 HOMO and MAPI valence band edge, our results for the mutually polarized interface point out the lack of a sufficient driving force for hole transport. While the hole mobility of HTM1 outperforms those of the other HTM molecules, for this HTM molecule, our findings suggest the application of lead halide perovskite compositions other than MAPI, with substituents that lower its valence band maximum potential value.

In Situ Formation of Zwitterionic Ligands: Changing the Passivation Paradigms of CsPbBr3 Nanocrystals.

CsPbBr3 nanocrystals (NCs) passivated by conventional lipophilic capping ligands suffer from colloidal and optical instability under ambient conditions, commonly due to the surface rearrangements induced by the polar solvents used for the NC purification steps. To avoid onerous postsynthetic approaches, ascertained as the only viable stability-improvement strategy, the surface passivation paradigms of as-prepared CsPbBr3 NCs should be revisited. In this work, the addition of an extra halide source (8-bromooctanoic acid) to the typical CsPbBr3 synthesis precursors and surfactants leads to the in situ formation of a zwitterionic ligand already before cesium injection. As a result, CsPbBr3 NCs become insoluble in nonpolar hexane, with which they can be washed and purified, and form stable colloidal solutions in a relatively polar medium (dichloromethane), even when longly exposed to ambient conditions. The improved NC stability stems from the effective bidentate adsorption of the zwitterionic ligand on the perovskite surfaces, as supported by theoretical investigations. Furthermore, the bidentate functionalization of the zwitterionic ligand enables the obtainment of blue-emitting perovskite NCs with high PLQYs by UV-irradiation in dichloromethane, functioning as the photoinduced chlorine source.

Unexpected Imidazole Coordination to the Dirhodium Center in a Protein Environment: Insights from X-ray Crystallography and Quantum Chemistry.

X-ray diffraction data demonstrate that the adduct formed upon the reaction of dirhodium(II,II) tetraacetate with RNase A reacts with imidazole, leading to the formation of an unexpected product with the imidazole that binds the dirhodium center at an equatorial site rather than an axial site. The origin of this result has been dissected using quantum-chemical calculations.

Challenges of modeling nanostructured materials for photocatalytic water splitting.

Understanding the water splitting mechanism in photocatalysis is a rewarding goal as it will allow producing clean fuel for a sustainable life in the future. However, identifying the photocatalytic mechanisms by modeling photoactive nanoparticles requires sophisticated computational techniques based on multiscale modeling. In this review, we will survey the strengths and drawbacks of currently available theoretical methods at different length and accuracy scales. Understanding the surface-active site through Density Functional Theory (DFT) using new, more accurate exchange-correlation functionals plays a key role for surface engineering. Larger scale dynamics of the catalyst/electrolyte interface can be treated with Molecular Dynamics albeit there is a need for more generalizations of force fields. Monte Carlo and Continuum Modeling techniques are so far not the prominent path for modeling water splitting but interest is growing due to the lower computational cost and the feasibility to compare the modeling outcome directly to experimental data. The future challenges in modeling complex nano-photocatalysts involve combining different methods in a hierarchical way so that resources are spent wisely at each length scale, as well as accounting for excited states chemistry that is important for photocatalysis, a path that will bring devices closer to the theoretical limit of photocatalytic efficiency.

TiO2-Based Nanostructures, Composites and Hybrid Photocatalysts.

The field of materials sciences has always been strongly interconnected with the most significant technological developments in the modern era, and such an interconnection is absolutely evident at least since the 1950s revolution of electronics and microelectronics, driven by advances in the science of semiconductors [...].

d-Glucose Adsorption on the TiO2 Anatase (100) Surface: A Direct Comparison Between Cluster-Based and Periodic Approaches.

Titanium dioxide (TiO2) has been extensively studied as a suitable material for a wide range of fields including catalysis and sensing. For example, TiO2-based nanoparticles are active in the catalytic conversion of glucose into value-added chemicals, while the good biocompatibility of titania allows for its application in innovative biosensing devices for glucose detection. A key process for efficient and selective biosensors and catalysts is the interaction and binding mode between the analyte and the sensor/catalyst surface. The relevant features regard both the molecular recognition event and its effects on the nanoparticle electronic structure. In this work, we address both these features by combining two first-principles methods based on periodic boundary conditions and cluster approaches (CAs). While the former allows for the investigation of extended materials and surfaces, CAs focus only on a local region of the surface but allow for using hybrid functionals with low computational cost, leading to a highly accurate description of electronic properties. Moreover, the CA is suitable for the study of reaction mechanisms and charged systems, which can be cumbersome with PBC. Here, a direct and detailed comparison of the two computational methodologies is applied for the investigation of d-glucose on the TiO2 (100) anatase surface. As an alternative to the commonly used PBC calculations, the CA is successfully exploited to characterize the formation of surface and subsurface oxygen vacancies and to determine their decisive role in d-glucose adsorption. The results of such direct comparison allow for the selection of an efficient, finite-size structural model that is suitable for future investigations of biosensor electrocatalytic processes and biomass conversion catalysis.