Cobalt-free layered perovskites RBaCuFeO5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction.

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 family RBaCuFeO5+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, Fe3+ is the transition metal cation the most prone to donate electrons. We also show that similar R3+/Ba2+ 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 (LaBaCuFeO5.49), 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.

Machine Learning for Quantitative Structural Information from Infrared Spectra: The Case of Palladium Hydride.

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.

Evidence of bifunctionality of carbons and metal atoms in catalyzed acetylene hydrochlorination.

Carbon supports are ubiquitous components of heterogeneous catalysts for acetylene hydrochlorination to vinyl chloride, from commercial mercury-based systems to more sustainable metal single-atom alternatives. Their potential co-catalytic role has long been postulated but never unequivocally demonstrated. Herein, we evidence the bifunctionality of carbons and metal sites in the acetylene hydrochlorination catalytic cycle. Combining operando X-ray absorption spectroscopy with other spectroscopic and kinetic analyses, we monitor the structure of single metal atoms (Pt, Au, Ru) and carbon supports (activated, non-activated, and nitrogen-doped) from catalyst synthesis, using various procedures, to operation at different conditions. Metal atoms exclusively activate hydrogen chloride, while metal-neighboring sites in the support bind acetylene. Resolving the coordination environment of working metal atoms guides theoretical simulations in proposing potential binding sites for acetylene in the support and a viable reaction profile. Expanding from single-atom to ensemble catalysis, these results reinforce the importance of optimizing both metal and support components to leverage the distinct functions of each for advancing catalyst design.

Deciphering the Mechanism of Crystallization of UiO-66 Metal-Organic Framework.

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.

Ti-Doping in Silica-Supported PtZn Propane Dehydrogenation Catalysts: From Improved Stability to the Nature of the Pt-Ti Interaction.

Propane dehydrogenation is an important industrial reaction to access propene, the world's second most used polymer precursor. Catalysts for this transformation are required to be long living at high temperature and robust toward harsh oxidative regeneration conditions. In this work, combining surface organometallic chemistry and thermolytic molecular precursor approach, we prepared well-defined silica-supported Pt and alloyed PtZn materials to investigate the effect of Ti-doping on catalytic performances. Chemisorption experiments and density functional calculations reveal a significant change in the electronic structure of the nanoparticles (NPs) due to the Ti-doping. Evaluation of the resulting materials PtZn/SiO2 and PtZnTi/SiO2 during long deactivation phases reveal a stabilizing effect of Ti in PtZnTi/SiO2 with a kd of 0.015 h-1 compared to PtZn/SiO2 with a kd of 0.022 h-1 over 108 h on stream. Such a stabilizing effect is also present during a second deactivation phase after applying a regeneration protocol to the materials under O2 and H2 at high temperatures. A combined scanning transmission electron microscopy, in situ X-ray absorption spectroscopy, electron paramagnetic resonance, and density functional theory study reveals that this effect is related to a sintering prevention of the alloyed PtZn NPs in PtZnTi/SiO2 due to a strong interaction of the NPs with Ti sites. However, in contrast to classical strong metal-support interaction, we show that the coverage of the Pt NPs with TiOx species is not needed to explain the changes in adsorption and reactivity properties. Indeed, the interaction of the Pt NPs with TiIII sites is enough to decrease CO adsorption and to induce a red-shift of the CO band because of electron transfer from the TiIII sites to Pt0.

Controlling the Strong Metal-Support Interaction Overlayer Structure in Pt/TiO2 Catalysts Prevents Particle Evaporation.

Platinum nanoparticles (NPs) supported by titania exhibit a strong metal-support interaction (SMSI)[1] that can induce overlayer formation and encapsulation of the NP's with a thin layer of support material. This encapsulation modifies the catalyst's properties, such as increasing its chemoselectivity[2] and stabilizing it against sintering.[3] Encapsulation is typically induced during high-temperature reductive activation and can be reversed through oxidative treatments.[1] However, recent findings indicate that the overlayer can be stable in oxygen.[4, 5] Using in situ transmission electron microscopy, we investigated how the overlayer changes with varying conditions. We found that exposure to oxygen below 400 °C caused disorder and removal of the overlayer upon subsequent hydrogen treatment. In contrast, elevating the temperature to 900 °C while maintaining the oxygen atmosphere preserved the overlayer, preventing platinum evaporation when exposed to oxygen. Our findings demonstrate how different treatments can influence the stability of nanoparticles with or without titania overlayers. expanding the concept of SMSI and enabling noble metal catalysts to operate in harsh environments without evaporation associated losses during burn-off cycling.

Origin of the Activity Trend in the Oxidative Dehydrogenation of Ethanol over VOx /CeO2.

Supported vanadia (VOx ) is a versatile catalyst for various redox processes where ceria-supported VOx 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 VOx /CeOx catalysts using operando quick V K- and Ce L3 - 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 Ce4+ /Ce3+ 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 VOx monolayer coverage), is related to the formation of spectator V4+ and Ce3+ species, which were identified here for the first time. These results might prove to be helpful for the rational optimization of VOx /CeO2 catalysts and the refinement of the theoretical models.

Reaction-Induced Formation of Stable Mononuclear Cu(I)Cl Species on Carbon for Low-Footprint Vinyl Chloride Production.

Copper catalysts are attractive candidates for Hg-free vinyl chloride monomer (VCM) production via acetylene hydrochlorination due to their non-toxic nature and high stability. However, the optimal architecture for Cu-based catalysts at the nanoscale is not yet fully understood. To address this gap, the metal precursor and the annealing temperature are modified to prepare copper nanoparticles or single atoms, either in chlorinated or ligand-free form, on an unmodified carbon support. Evaluation in the reaction reveals a remarkable convergence of the performance of all materials to the stable VCM productivity of the single-atom catalyst. In-depth characterization by advanced microscopy, quasi in situ and operando spectroscopy, and simulations uncover a reaction-induced formation of low-valent, single atom Cu(I)Cl site motif, regardless of the initial nanostructure. Various surface oxygen groups promote nanoparticle redispersion by stabilizing single-atom CuClx species. The anchoring site structure does not strongly influence the acetylene adsorption energy or the crucial role they play in stabilizing key reaction intermediates. A life-cycle assessment demonstrates the potential environmental benefits of copper catalysts over state-of-the-art alternatives. This work contributes to a better understanding of optimal metal speciation and highlights the sustainability of Cu-based catalysts for VCM production.

Optimizing the Pd Sites in Pure Metallic Aerogels for Efficient Electrocatalytic H2 O2 Production.

Decentralized electrochemical production of hydrogen peroxide (H2 O2 ) is an attractive alternative to the industrial anthraquinone process, the application of which is hindered by the lack of high-performance electrocatalysts in acidic media. Herein, a novel catalyst design strategy is reported to optimize the Pd sites in pure metallic aerogels by tuning their geometric environments and electronic structures. By increasing the Hg content in the Pd-Hg aerogels, the PdPd coordination is gradually diminished, resulting in isolated, single-atom-like Pd motifs in the Pd2 Hg5 aerogel. Further heterometal doping leads to a series of M-Pd2 Hg5 aerogels with an unalterable geometric environment, allowing for sole investigation of the electronic effects. Combining theoretical and experimental analyses, a volcano relationship is obtained for the M-Pd2 Hg5 aerogels, demonstrating an effective tunability of the electronic structure of the Pd active sites. The optimized Au-Pd2 Hg5 aerogel exhibits an outstanding H2 O2 selectivity of 92.8% as well as transferred electron numbers of ≈2.1 in the potential range of 0.0-0.4 VRHE . This work opens a door for designing metallic aerogel electrocatalysts for H2 O2 production and highlights the importance of electronic effects in tuning electrocatalytic performances.

Spectroscopy vs. Electrochemistry: Catalyst Layer Thickness Effects on Operando/In Situ Measurements.

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.

Molecular Dynamics and Structural Studies of Zinc Chloroquine Complexes.

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 Zn2+ through the quinoline ring nitrogen, forming [Zn(CQH)Clx(H2O)3-x](3+)-x (x = 0, 1, 2, and 3) tetrahedral complexes. The Zn(CQH)Cl3 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)(H2O)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.

BCC-Cu nanoparticles: from a transient to a stable allotrope by tuning size and reaction conditions.

Metallic copper generally adopts an FCC structure. In this work, we detect highly unusual BCC-structured Cu nanoparticles as a transient intermediate during the H2 reduction of a CuI precursor, [Cu4OtBu4], grafted onto the surface of partially dehydroxylated silica. The Cu BCC structure, assigned by in situ Cu K-edge XANES and EXAFS, as well as in situ synchrotron PXRD, converts upon heating into the most commonly found FCC allotrope. DFT calculations show that the BCC-Cu phase is in fact predicted to be more stable for small particles, and that their stability increases at lower H2 concentrations. Using this knowledge, we show that it is possible to synthesize BCC-structured Cu nanoparticles as a stable allotrope by reduction of the same grafted precursor either in 10% H2 diluted in Ar or 100% H2 at low temperature.

Hydrothermal synthesis of multi-cationic high-entropy layered double hydroxides.

High-entropy materials are compositionally complex materials which often contain five or more elements. The most commonly studied materials in this field are alloys and oxides, where their composition allows for tunable materials properties. High-entropy layered double hydroxides have been recently touted as the next focus for the field of high-entropy materials to expand into. However, most previous work on multi-cationic layered double hydroxides has focused on syntheses with 5 or less cations in the structure. To bridge this gap into high-entropy materials, this work explores the range and extent of different compositional combinations for high-entropy double layered hydroxides. Specifically, pure layered double hydroxides were synthesized with different combinations of 7 cations (Mg, Co, Cu, Zn, Ni, Al, Fe, Cr) as well as one combination of 8 cations by utilizing a hydrothermal synthesis method. Furthermore, magnetic properties of the 8-cation LDH were investigated.

Beware of beam damage under reaction conditions: X-ray induced photochemical reduction of supported VOx catalysts during in situ XAS experiments.

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 (VOx) 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 VOx 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.

Chloroquine disrupts zinc storage granules in primary Malpighian tubule cells of Drosophila melanogaster.

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.

A Robust and Efficient Propane Dehydrogenation Catalyst from Unexpectedly Segregated Pt2Mn Nanoparticles.

The increasing demand for short chain olefins like propene for plastics production and the availability of shale gas make the development of highly performing propane dehydrogenation (PDH) catalysts, robust toward industrially applied harsh regeneration conditions, a highly important field of research. A combination of surface organometallic chemistry and thermolytic molecular precursor approach was used to prepare a nanometric, bimetallic Pt-Mn material (3 wt % Pt, 1.3 wt % Mn) supported on silica via consecutive grafting of a Mn and Pt precursor on surface OH groups present on the support surface, followed by a treatment under a H2 flow at high temperature. The material exhibits a 70% fraction of the overall Mn as MnII single sites on the support surface; the remaining Mn is incorporated in segregated Pt2Mn nanoparticles. The material shows great performance in PDH reaction with a low deactivation rate. In particular, it shows outstanding robustness during repeated regeneration cycles, with conversion and selectivity stabilizing at ca. 37 and 98%, respectively. Notably, a material with a lower Pt loading of only 0.05 wt % shows an outstanding catalytic performance─initial productivity of 4523 gC3H6/gPt h and an extremely low kd of 0.003 h-1 under a partial pressure of H2, which are among the highest reported productivities. A combined in situ X-ray absorption spectroscopy, scanning transmission electron microscopy, electron paramagnetic resonance, and metadynamics at the density functional theory level study could show that the strong interaction between the MnII-decorated support and the unexpectedly segregated Pt2Mn particles is most likely responsible for the outstanding performance of the investigated materials.

Tryptophan regulates Drosophila zinc stores.

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 insect­a 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-hydroxykynurenine­zinc­chloride complex, precipitating within the storage granules. Thus, zinc and the kynurenine pathway­well-known modulators of immunity, blood pressure, aging, and neurodegeneration­are physiologically connected.

Redox Dynamics of Active VO x Sites Promoted by TiO x during Oxidative Dehydrogenation of Ethanol Detected by Operando Quick XAS.

Titania-supported vanadia (VO x /TiO2) 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% V2O5/15% TiO2/SiO2 catalyst (consisting of submonolayer VO x species anchored onto a TiO x monolayer, which in turn is supported on SiO2) during the oxidative dehydrogenation of ethanol. The VO x species in 5% V2O5/15% TiO2/SiO2 show high selectivity to acetaldehyde and an ca. 40 times higher acetaldehyde formation rate in comparison to VO x species supported on SiO2 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% V2O5/15% TiO2/SiO2 is kinetically coupled to the formation of a V4+ intermediate, while the formation of V3+ is delayed and 10-70 times slower. The low-coordinated nature of various redox states of VO x species (V5+, V4+, and V3+) in the 5% V2O5/15% TiO2/SiO2 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 Ti4+/Ti3+ 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.

Redispersion strategy for high-loading carbon-supported metal catalysts with controlled nuclearity.

Supported low-nuclearity metal catalysts integrating single atoms or small clusters have emerged as promising materials for diverse applications. While sophisticated synthetic methods provide a high level of nuclearity control in the subnanometre regime, these routes do not fulfil the requirements for translation into industrial practice of (i) effectiveness for high metal contents and (ii) facile scalability. Herein, we present a gas-phase redispersion strategy consisting of sequential C2H2 and HCl treatments to gradually disperse Ru, Rh and Ir nanoparticles supported on commercial activated carbon with metal content up to 10 wt% and initial average sizes of ≈ 1 nm into small clusters and eventually single atoms. Avoidance of nanoparticle surface overchlorination, which hinders C2H2 adsorption, is identified as key for the redispersion process, as demonstrated by the inefficacy of both C2H2-HCl cofeeding and inverse sequence (i.e., HCl first) treatments. Precise size control (±0.1 nm) is enabled by regulating the number of C2H2-HCl cycles. Detailed characterisation by X-ray absorption spectroscopy, electron paramagnetic resonance and time-resolved mass spectrometry reveals that the redispersion occurs via a layer-by-layer mechanism. Specifically, the migration of surface chlorinated metal species to the carbon support is induced by the C2H2 treatment, depleting accessible surface Cl atoms, while the subsequent HCl treatment rechlorinates the cluster surface. The strategy paves the way for the generation of high-density metal sites with tuneable nuclearity for tailored applications.

Performance descriptors of nanostructured metal catalysts for acetylene hydrochlorination.

Controlling the precise atomic architecture of supported metals is central to optimizing their catalytic performance, as recently exemplified for nanostructured platinum and ruthenium systems in acetylene hydrochlorination, a key process for vinyl chloride production. This opens the possibility of building on historically established activity correlations. In this study, we derived quantitative activity, selectivity and stability descriptors that account for the metal-dependent speciation and host effects observed in acetylene hydrochlorination. To achieve this, we generated a platform of Au, Pt, Ru, Ir, Rh and Pd single atoms and nanoparticles supported on different types of carbon and assessed their evolution during synthesis and under the relevant reaction conditions. Combining kinetic, transient and chemisorption analyses with modelling, we identified the acetylene adsorption energy as a speciation-sensitive activity descriptor, further determining catalyst selectivity with respect to coke formation. The stability of the different nanostructures is governed by the interplay between single atom-support interactions and chlorine affinity, promoting metal redispersion or agglomeration, respectively.