Antimony‐based perovskite‐inspired materials (PIMs) are solution‐processable halide absorbers with interesting optoelectronic properties, low toxicity, and good intrinsic stability. Their bandgaps around 2 eV make them particularly suited for indoor photovoltaics (IPVs). Yet, so far only the fully inorganic Cs3Sb2ClxI9−x composition has been employed as a light‐harvesting layer in IPVs. Herein, the first triple‐cation Sb‐based PIM (CsMAFA‐Sb) in which the A‐site of the A3Sb2X9 structure consists of inorganic cesium alloyed with organic methylammonium (MA) and formamidinium (FA) cations is introduced. Simultaneously, the X‐site is tuned to guarantee a 2D structure while keeping the bandgap nearly unchanged. The presence of three A‐site cations is essential to reduce the trap‐assisted recombination pathways and achieve high performance in both outdoor and indoor photovoltaics. The external quantum efficiency peak of 77% and the indoor power conversion efficiency of 6.4% are the highest values ever reported for pnictohalide‐based photovoltaics. Upon doping of the P3HT hole‐transport layer with F4‐TCNQ, the power conversion efficiency of CsMAFA‐Sb devices is fully retained compared to the initial value after nearly 150 days of storage in dry air. This work provides an effective compositional strategy to inspire new perspectives in the PIM design for IPVs with competitive performance and air stability.

CsPbBr 3 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 CsPbBr 3 NCs should be revisited. In this work, the addition of an extra halide source (8-bromooctanoic acid) to the typical CsPbBr 3 synthesis precursors and surfactants leads to the in situ formation of a zwitterionic ligand already before cesium injection. As a result, CsPbBr 3 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.

TiO2 anatase is a functional material that is exploited in several technological devices from photovoltaics to energy storage, water splitting, and solar-to-fuel photocatalysis. In this context, numerous theoretical studies addressed the interaction of water with the most stable anatase (101) surface and reported undissociated molecular adsorption. However, recent experiments on such surface facet at low water coverage pointed out the presence of OH groups. Motivated by these findings, we report here a first-principles investigation on the adsorption and dissociation at low (θ = 0.25) and full (θ = 1) coverage of the first water monolayer at the (101) anatase surface at 300 K with metadynamics. Our simulations show barrierless water adsorption, and at the same time, the dynamic nature of titania–water interactions allows for the dissociation of water and the possible formation of a partial hydroxylated surface at room temperature. These results highlight the relevance of dynamic in modeling surface–water interactions and provide new insights into the physicochemical properties of the pristine anatase TiO2(101) surface in an aqueous environment.

Na-ion batteries (NIBs) are promising devices for large-scale energy-storage facilities. Nanostructured TiO2 is an efficient NIB negative electrode, showing good cycling performance and rate capability, but its activity depends on the crystalline facets exposed by anatase nanoparticles. Hence, we propose here a DFT+U study of Na+ adsorption and insertion at (101), (100) and (001)-TiO2 surfaces under the influence of external electric fields, which are simulated by adding a sawtooth-like electrostatic potential to the bare ionic potential. We find that field polarization affects Na+ uptake as well as titania electronic features, promoting redox processes within Ti sublattice, as in battery charge/discharge cycling. Our results highlight the high-energy (001) surface to be the most active, for both directions of external fields, proving its activity to be exerted reversibly. Besides further insights, these outcomes pave the route for further exploration and design of electrode materials by simulation of battery in operando conditions. Graphical Abstract

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.

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Engineering the solid-electrolyte interphase (SEI) with purposely designed molecules represents a promising strategy to achieve durable and effective anodes for lithium metal batteries (LMBs). The use of vinylene carbonate (VC)...

Li-air batteries are a promising energy storage technology for large-scale applications, but the release of highly reactive singlet oxygen ( 1 O 2 ) during battery operation represents a main concern that sensibly limits their effective deployment. An indepth understanding of the reaction mechanisms underlying the 1 O 2 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 1 O 2 at the Li 2 O 2 surface during oxidation, i.e., the battery charging process. Based on recent hypothesis, we depict a feasible O 2 2− /O 2 − /O 2 mechanisms occurring from the (112̅ 0)−Li 2 O 2 surface termination. Our highly accurate calculations allow for the identification of a stable superoxide as local minimum along the potential energy surface (PES) for 1 O 2 release, which is not detected by periodic DFT. We find that 1 O 2 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 Li 2 O 2 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 1 O 2 for new and highly performing Li-air batteries.