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The compositional tunability of non-isovalent multicomponent chalcogenide thin films and the extent of atomic ordering of their crystal structure is key to the performance of many modern technologies. In contrast, the effects of ordering are rarely studied for quantum-confined materials, such as colloidal nanocrystals. In this paper, the possibilities around composition tunability and atomic ordering are explored in ultrasmall ternary and quaternary quantum dots, taking I-III-VI-group Cu-Zn-In-Se semiconductor as a case study. A quantitative synthesis for 3.3 nm quaternary chalcogenide nanocrystals is developed and shown that cation and cationic vacancy ordering can be achieved in these systems consisting of only 100s of atoms. Combining experiment and theoretical calculations, the relationship between structural ordering and optical properties of the materials are demonstrated. It is found that the arrangement and ordering of cationic sublattice plays an important role in the luminescent efficiency. Specifically, the concentration of Cu-vacancy couples in the nanocrystal correlates with luminescence quantum yield, while structure ordering increases the occurrence of such optically active Cu-vacancy units. On the flip side, the detrimental impact of cationic site disorder in I-III-VI nanocrystals can be mitigated by introducing a cation of intermediate valence, such as Zn (II)., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Restructuring of metal components on bimetallic nanoparticle surfaces in response to the changes in reactive environment is a ubiquitous phenomenon whose potential for the design of tunable catalysts is underexplored. The main challenge is the lack of knowledge of the structure, composition, and evolution of species on the nanoparticle surfaces during reaction. We apply a modulation excitation approach to the X-ray absorption spectroscopy of the 30 atomic % Pd in Au supported nanocatalysts via the gas (H 2 and O 2 ) concentration modulation. For interpreting restructuring kinetics, we correlate the phase-sensitive detection with the time-domain analysis aided by a denoising algorithm. Here we show that the surface and near-surface species such as Pd oxides and atomically dispersed Pd restructured periodically, featuring different time delays. We propose a model that Pd oxide formation is preceded by the build-up of Pd regions caused by oxygen-driven segregation of Pd atoms towards the surface. During the H 2 pulse, rapid reduction and dissolution of Pd follows an induction period which we attribute to H 2 dissociation. Periodic perturbations of nanocatalysts by gases can, therefore, enable variations in the stoichiometry of the surface and near-surface oxides and dynamically tune the degree of oxidation/reduction of metals at/near the catalyst surface., (© 2024. The Author(s).)

Evolution of the Pd active centers in size and spatial distribution leads to an irreversible deactivation in many high-temperature catalytic processes. This research demonstrates the use of a defective alumina (Al 2 O 3-x ) as catalyst support to anchor Pd atoms and suppress the growth of Pd clusters in catalytic methane oxidation. A combination of operando spectroscopy and density functional theory (DFT) calculations provide insights into the evolution of Pd species and reveals distinct catalytic methane oxidation mechanisms on Pd single atoms, clusters, and nanoparticles (NPs). Among these Pd species, the cluster active centers are found to be the most favorable participants in methane oxidation due to their high dispersion, high content of Pd 2+ oxidation state, and resistance to deactivation by carbonates, bicarbonates, and water. The Pd/Al 2 O 3-x catalyst shows increased stability with respect to a Pd/Al 2 O 3 counterpart during simulated aging in alternating reducing and oxidizing conditions due to stronger interactions with the support. This study demonstrates that defect engineering of non-reducible supports can constrain the evolution of active centers, which holds promising potential for widespread utilization across diverse industrial catalytic processes, including various hydrogenation and oxidation reactions., (© 2024. The Author(s).)

Infrared spectroscopy (IR) is a widely used technique enabling to identify specific functional groups in the molecule of interest based on their characteristic vibrational modes or the presence of a specific adsorption site based on the characteristic vibrational mode of an adsorbed probe molecule. The interpretation of an IR spectrum is generally carried out within a fingerprint paradigm by comparing the observed spectral features with the features of known references or theoretical calculations. This work demonstrates a method for extracting quantitative structural information beyond this approach by application of machine learning (ML) algorithms. Taking palladium hydride formation as an example, Pd-H pressure-composition isotherms are reconstructed using IR data collected in situ in diffuse reflectance using CO molecule as a probe. To the best of the knowledge, this is the first example of the determination of continuous structural descriptors (such as interatomic distance and stoichiometric coefficient) from the fine structure of vibrational spectra, which opens new possibilities of using IR spectra for structural analysis., (© 2024 The Authors. Small Methods published by Wiley‐VCH GmbH.)

Understanding structure-performance relationships are essential for the rational design of new functional materials or in the further optimization of (catalytic) processes. Due to the high penetration depth of the radiation used, synchrotron-based hard X-ray techniques (with energy > 4.5 keV) allow the study of materials under realistic conditions (in situ and operando) and thus play an important role in uncovering structure-performance relationships. X-ray absorption and emission spectroscopies (XAS and XES) give insight into the electronic structure (oxidation state, spin state) and local geometric structure (type and number of nearest neighbor atoms, bond distances, disorder) up to ~5 Å around the element of interest. In this mini review, we will give an overview of the in situ and operando capabilities of the SuperXAS beamline, a facility for hard X-ray spectroscopy, through recent examples from studies of heterogeneous catalysts, electrochemical systems, and photoinduced processes. The possibilities for time-resolved experiments in the time range from ns to seconds and longer are illustrated. The extension of X-ray spectroscopy at the new Debye beamline combined with operando X-ray scattering and diffraction and further developments of time-resolved XES at SuperXAS will open new possibilities after the Swiss Light Source upgrade mid 2025., (Copyright 2024 Aram Bugaev, Adam H. Clark, Nina S. Genz, Olga V. Safonova, Grigory Smolentsev, Maarten Nachtegaal. License: This work is licensed under a Creative Commons Attribution 4.0 International License.)

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO 3 and LaFeO 3 /LaNiO 3 thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive La 0.67 Sr 0.33 MnO 3 layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer Ca 2 Nb 3 O 10 nanosheet-buffered 100 nm SiN x membranes. The in situ Fe and Ni K-edges XAS spectra were measured from the backside of the SiN x membrane using fluorescence yield detection under electrocatalytic reaction conditions. The XAS spectra show significant spectral changes, which indicate that (1) the metal (co)valencies increase, and (2) the number of 3d electrons remains constant with applied potential. We find that the whole 8 unit cells react to the potential changes, including the buried LaNiO 3 film., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Zirconium-containing metal-organic framework (MOF) with UiO-66 topology is an extremely versatile material, which finds applications beyond gas separation and catalysis. However, after more than 10 years after the first reports introducing this MOF, understanding of the molecular-level mechanism of its nucleation and growth is still lacking. By means of in situ time-resolved high-resolution mass spectrometry, Zr K-edge X-ray absorption spectroscopy, magic-angle spinning nuclear magnetic resonance spectroscopy, and X-ray diffraction it is showed that the nucleation of UiO-66 occurs via a solution-mediated hydrolysis of zirconium chloroterephthalates, whose formation appears to be autocatalytic. Zirconium-oxo nodes form directly and rapidly during the synthesis, the formation of pre-formed clusters and stable non-stoichiometric intermediates are not observed. The nuclei of UiO-66 possess identical to the crystals local environment, however, they lack long-range order, which is gained during the crystallization. Crystal growth is the rate-determining step, while fast nucleation controls the formation of the small crystals of UiO-66 with a narrow size distribution of about 200 nanometers., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Co-based perovskite oxides are intensively studied as promising catalysts for electrochemical water splitting in an alkaline environment. However, the increasing Co demand by the battery industry is pushing the search for Co-free alternatives. Here we report a systematic study of the Co-free layered perovskite famil y RBaCuFeO 5+ δ (R = 4f lanthanide), where we uncover the existence of clear correlations between electrochemical properties and several physicochemical descriptors. Using a combination of advanced neutron and X-ray synchrotron techniques with ab initio DFT calculations we demonstrate and rationalize the positive impact of a large R ionic radius in their oxygen evolution reaction (OER) activity. We also reveal that, in these materials, Fe 3+ is the transition metal cation the most prone to donate electrons. We also show that similar R 3+ /Ba 2+ ionic radii favor the incorporation and mobility of oxygen in the layered perovskite structure and increase the number of available O diffusion paths, which have an additional, positive impact on both, the electric conductivity and the OER process. An unexpected result is the observation of a clear surface reconstruction exclusively in oxygen-rich samples ( δ > 0), a fact that could be related to their superior OER activity. The encouraging intrinsic OER values obtained for the most active electrocatalyst (LaBaCuFeO 5.49 ), together with the possibility of industrially producing this material in nanocrystalline form should inspire the design of other Co-free oxide catalysts with optimal properties for electrochemical water splitting., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Supported vanadia (VO x ) is a versatile catalyst for various redox processes where ceria-supported VO x have shown to be particularly active in the oxidative dehydrogenation (ODH) of alcohols. In this work, we clarify the origin of the volcano-shaped ethanol ODH activity trend for VO x /CeO x catalysts using operando quick V K- and Ce L 3 - edge XAS experiments performed under transient conditions. We quantitatively demonstrate that both vanadium and cerium are synergistically involved in alcohol ODH. The concentration of reversible Ce 4+ /Ce 3+ species was identified as the main descriptor of the alcohol ODH activity. The activity drop in the volcano plot, observed at above ca. 3 V nm -2 surface loading (ca. 30 % of VO x monolayer coverage), is related to the formation of spectator V 4+ and Ce 3+ species, which were identified here for the first time. These results might prove to be helpful for the rational optimization of VO x /CeO 2 catalysts and the refinement of the theoretical models., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In recent years, operando/in situ X-ray absorption spectroscopy (XAS) has become an important tool in the electrocatalysis community. However, the high catalyst loadings often required to acquire XA-spectra with a satisfactory signal-to-noise ratio frequently imply the use of thick catalyst layers (CLs) with large ion- and mass-transport limitations. To shed light on the impact of this variable on the spectro-electrochemical results, in this study we investigate Pd-hydride formation in carbon-supported Pd-nanoparticles (Pd/C) and an unsupported Pd-aerogel with similar Pd surface areas but drastically different morphologies and electrode packing densities. Our in situ XAS and rotating disk electrode (RDE) measurements with different loadings unveil that the CL-thickness largely determines the hydride formation trends inferred from spectro-electrochemical experiments, therewith calling for the minimization of the CL-thickness in such experiments and the use of complementary thin-film control measurements., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Cu 2 S is a promising solar energy conversion material due to its suitable optical properties, high elemental earth abundance, and nontoxicity. In addition to the challenge of multiple stable secondary phases, the short minority carrier diffusion length poses an obstacle to its practical application. This work addresses the issue by synthesizing nanostructured Cu 2 S thin films, which enables increased charge carrier collection. A simple solution-processing method involving the preparation of CuCl and CuCl 2 molecular inks in a thiol-amine solvent mixture followed by spin coating and low-temperature annealing was used to obtain phase-pure nanostructured (nanoplate and nanoparticle) Cu 2 S thin films. The photocathode based on the nanoplate Cu 2 S (FTO/Au/Cu 2 S/CdS/TiO 2 /RuO x ) reveals enhanced charge carrier collection and improved photoelectrochemical water-splitting performance compared to the photocathode based on the non-nanostructured Cu 2 S thin film reported previously. A photocurrent density of 3.0 mA cm -2 at -0.2 versus a reversible hydrogen electrode ( V RHE ) with only 100 nm thickness of a nanoplate Cu 2 S layer and an onset potential of 0.43 V RHE were obtained. This work provides a simple, cost-effective, and high-throughput method to prepare phase-pure nanostructured Cu 2 S thin films for scalable solar hydrogen production., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Chloroquine (CQ) is a first-choice drug against malaria and autoimmune diseases. It has been co-administered with zinc against SARS-CoV-2 and soon dismissed because of safety issues. The structural features of Zn-CQ complexes and the effect of CQ on zinc distribution in cells are poorly known. In this study, state-of-the-art computations combined with experiments were leveraged to solve the structural determinants of zinc-CQ interactions in solution and the solid state. NMR, ESI-MS, and X-ray absorption and diffraction methods were combined with ab initio molecular dynamics calculations to address the kinetic lability of this complex. Within the physiological pH range, CQ binds Zn 2+ through the quinoline ring nitrogen, forming [Zn(CQH)Cl x (H 2 O) 3- x ] (3+)- x ( x = 0, 1, 2, and 3) tetrahedral complexes. The Zn(CQH)Cl 3 species is stable at neutral pH and at high chloride concentrations typical of the extracellular medium, but metal coordination is lost at a moderately low pH as in the lysosomal lumen. The pentacoordinate complex [Zn(CQH)(H 2 O) 4 ] 3+ may exist in the absence of chloride. This in vitro / in silico approach can be extended to other metal-targeting drugs and bioinorganic systems.

Operando X-ray absorption spectroscopy identified that the concentration of Fe 2+ species in the working state-of-the-art Pt-FeO x catalysts quantitatively correlates to their preferential carbon monoxide oxidation steady-state reaction rate at ambient temperature. Deactivation of such catalysts with time on stream originates from irreversible oxidation of active Fe 2+ sites. The active Fe 2+ species are presumably Fe +2 O -2 clusters in contact with platinum nanoparticles; they coexist with spectator trivalent oxidic iron (Fe 3+ ) and metallic iron (Fe 0 ) partially alloyed with platinum. The concentration of active sites and, therefore, the catalyst activity strongly depends on the pretreatment conditions. Fe 2+ is the resting state of the active sites in the preferential carbon monoxide oxidation cycle., (© 2022 Wiley-VCH GmbH.)

Contrasting reports exist in the literature regarding the effect of chloroquine treatment on cellular zinc uptake or secretion. Here, we tested the effect of chloroquine administration in the Drosophila model organism. We show that larvae grown on a diet supplemented with 2.5 mg/ml chloroquine lose up to 50% of their stored zinc and around 10% of their total potassium content. This defect in chloroquine-treated animals correlates with the appearance of abnormal autophagolysosomes in the principal cells of the Malpighian tubules, where zinc storage granules reside. We further show that the reported increase of Fluozin-3 fluorescence following treatment of cells with 300 μM chloroquine for 1 h may not reflect increased zinc accumulation, since a similar treatment in Madin-Darby canine kidney cells results in a 36% decrease in their total zinc content. Thus, chloroquine should not be considered a zinc ionophore. Zinc supplementation plus chloroquine treatment restored zinc content both in vivo and in vitro, without correcting autophagic or other ionic alterations, notably in potassium, associated with the chloroquine treatment. We suggest that chloroquine or hydroxychloroquine administration to patients could reduce intracellular zinc storage pools and be part of the drug's mechanism of action., (© The Author(s) 2022. Published by Oxford University Press.)

In situ X-ray absorption spectroscopy (XAS) is a powerful technique for the investigation of heterogeneous catalysts and electrocatalysts. The obtained XAS spectra are usually interpreted from the point of view of the investigated chemical processes, thereby sometimes omitting the fact that intense X-ray irradiation may induce additional transformations in metal speciation and, thus, in the corresponding XAS spectra. In this work, we report on X-ray induced photochemical reduction of vanadium in supported vanadia (VO x ) catalysts under reaction conditions, detected at a synchrotron beamline. While this process was not observed in an inert atmosphere and in the presence of water vapor, it occurred at room temperature in the presence of a reducing agent (ethanol or hydrogen) alone or mixed with oxygen. Temperature programmed experiments have shown that X-ray induced reduction of VO x species appeared very clear at 30-100 °C but was not detected at higher temperatures, where the thermocatalytic ethanol oxidative hydrogenation (ODH) takes place. Similar to other studies on X-ray induced effects, we suggest approaches, which can help to mitigate vanadium photoreduction, including defocusing of the X-ray beam and attenuation of the X-ray beam intensity by filters. To recognize beam damage under in situ / operando conditions, we suggest performing X-ray beam switching (on and off) tests at different beam intensities under in situ conditions.

Zinc deficiency is commonly attributed to inadequate absorption of the metal. Instead, we show that body zinc stores in Drosophila melanogaster depend on tryptophan consumption. Hence, a dietary amino acid regulates zinc status of the whole insect—a finding consistent with the widespread requirement of zinc as a protein cofactor. Specifically, the tryptophan metabolite kynurenine is released from insect fat bodies and induces the formation of zinc storage granules in Malpighian tubules, where 3-hydroxykynurenine and xanthurenic acid act as endogenous zinc chelators. Kynurenine functions as a peripheral zinc-regulating hormone and is converted into a 3-hydroxykynurenine–zinc–chloride complex, precipitating within the storage granules. Thus, zinc and the kynurenine pathway—well-known modulators of immunity, blood pressure, aging, and neurodegeneration—are physiologically connected.

Titania-supported vanadia (VO x /TiO 2 ) catalysts exhibit outstanding catalytic in a number of selective oxidation and reduction processes. In spite of numerous investigations, the nature of redox transformations of vanadium and titanium involved in various catalytic processes remains difficult to detect and correlate to the rate of products formation. In this work, we studied the redox dynamics of active sites in a bilayered 5% V 2 O 5 /15% TiO 2 /SiO 2 catalyst (consisting of submonolayer VO x species anchored onto a TiO x monolayer, which in turn is supported on SiO 2 ) during the oxidative dehydrogenation of ethanol. The VO x species in 5% V 2 O 5 /15% TiO 2 /SiO 2 show high selectivity to acetaldehyde and an ca. 40 times higher acetaldehyde formation rate in comparison to VO x species supported on SiO 2 with a similar density. Operando time-resolved V and Ti K-edge X-ray absorption near-edge spectroscopy, coupled with a transient experimental strategy, quantitatively showed that the formation of acetaldehyde over 5% V 2 O 5 /15% TiO 2 /SiO 2 is kinetically coupled to the formation of a V 4+ intermediate, while the formation of V 3+ is delayed and 10-70 times slower. The low-coordinated nature of various redox states of VO x species (V 5+ , V 4+ , and V 3+ ) in the 5% V 2 O 5 /15% TiO 2 /SiO 2 catalyst is confirmed using the extensive database of V K-edge XANES spectra of standards and specially synthesized molecular crystals. Much weaker redox activity of the Ti 4+ /Ti 3+ couple was also detected; however, it was found to not be kinetically coupled to the rate-determining step of ethanol oxidation. Thus, the promoter effect of TiO x is rather complex. TiO x species might be involved in a fast electron transport between VO x species and might affect the electronic structure of VO x , thereby promoting their reducibility. This study demonstrates the high potential of element-specific operando X-ray absorption spectroscopy for uncovering complex catalytic mechanisms involving the redox kinetics of various metal oxides., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Cu diimine complexes present a noble metal free alternative to classical Ru, Re, Ir and Pt based photosensitizers in solution photochemistry, photoelectrochemical or dye-sensitized solar cells. Optimization of these dyes requires understanding of factors governing the key photochemical properties: excited state lifetime and emission quantum yield. The involvement of exciplex formation in the deactivation of the photoexcited state is a key question. We investigate the excited-state structure of [Cu(dmp) 2 ] + and [Cu(dsbtmp) 2 ] + (dmp = 2,9-dimethyl-1,10-phenanthroline, dsbtmp = 2,9-di- sec -butyl-3,4,7,8-tetramethyl-1,10-phenanthroline) using pump-probe X-ray absorption spectroscopy (XAS) and DFT. Features of XAS that distinguish flattened tetrahedral site and 5-coordinated geometry with an additional solvent near Cu(II) center are identified. Pump-probe XAS demonstrates that for both complexes the excited state is 4-coordinated. For [Cu(dmp) 2 ] + the exciplex is 0.24 eV higher in energy than the flattened triplet state, therefore it can be involved in deactivation pathways as a non-observable state that forms slower than it decays. For [Cu(dsbtmp) 2 ] + the excited-state structure is characterized by Cu-N distances of 1.98 and 2.07 Å and minor distortions, leading to a 3 orders of magnitude longer excited-state lifetime.

Some fundamental concepts of catalysis are not fully explained but are of paramount importance for the development of improved catalysts. An example is the concept of structure insensitive reactions, where surface-normalized activity does not change with catalyst metal particle size. Here we explore this concept and its relation to surface reconstruction on a set of silica-supported Ni metal nanoparticles (mean particle sizes 1-6 nm) by spectroscopically discerning a structure sensitive (CO 2 hydrogenation) from a structure insensitive (ethene hydrogenation) reaction. Using state-of-the-art techniques, inter alia in-situ STEM, and quick-X-ray absorption spectroscopy with sub-second time resolution, we have observed particle-size-dependent effects like restructuring which increases with increasing particle size, and faster restructuring for larger particle sizes during ethene hydrogenation while for CO 2 no such restructuring effects were observed. Furthermore, a degree of restructuring is irreversible, and we also show that the rate of carbon diffusion on, and into nanoparticles increases with particle size. We finally show that these particle size-dependent effects induced by ethene hydrogenation, can make a structure sensitive reaction (CO 2 hydrogenation), structure insensitive. We thus postulate that structure insensitive reactions are actually apparently structure insensitive, which changes our fundamental understanding of the empirical observation of structure insensitivity., (© 2021. The Author(s).)