Showing papers by "Fritz Haber Institute of the Max Planck Society published in 2021"

In Situ/Operando Electrocatalyst Characterization by X-ray Absorption Spectroscopy

Abstract: During the last decades, X-ray absorption spectroscopy (XAS) has become an indispensable method for probing the structure and composition of heterogeneous catalysts, revealing the nature of the active sites and establishing links between structural motifs in a catalyst, local electronic structure, and catalytic properties. Here we discuss the fundamental principles of the XAS method and describe the progress in the instrumentation and data analysis approaches undertaken for deciphering X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra. Recent usages of XAS in the field of heterogeneous catalysis, with emphasis on examples concerning electrocatalysis, will be presented. The latter is a rapidly developing field with immense industrial applications but also unique challenges in terms of the experimental characterization restrictions and advanced modeling approaches required. This review will highlight the new insight that can be gained with XAS on complex real-world electrocatalysts including their working mechanisms and the dynamic processes taking place in the course of a chemical reaction. More specifically, we will discuss applications of in situ and operando XAS to probe the catalyst’s interactions with the environment (support, electrolyte, ligands, adsorbates, reaction products, and intermediates) and its structural, chemical, and electronic transformations as it adapts to the reaction conditions.

Revealing the CO Coverage-Driven C-C Coupling Mechanism for Electrochemical CO 2 Reduction on Cu 2 O Nanocubes via Operando Raman Spectroscopy.

Abstract: Electrochemical reduction of carbon dioxide (CO2RR) is an attractive route to close the carbon cycle and potentially turn CO2 into valuable chemicals and fuels. However, the highly selective generation of multicarbon products remains a challenge, suffering from poor mechanistic understanding. Herein, we used operando Raman spectroscopy to track the potential-dependent reduction of Cu2O nanocubes and the surface coverage of reaction intermediates. In particular, we discovered that the potential-dependent intensity ratio of the Cu-CO stretching band to the CO rotation band follows a volcano trend similar to the CO2RR Faradaic efficiency for multicarbon products. By combining operando spectroscopic insights with Density Functional Theory, we proved that this ratio is determined by the CO coverage and that a direct correlation exists between the potential-dependent CO coverage, the preferred C-C coupling configuration, and the selectivity to C2+ products. Thus, operando Raman spectroscopy can serve as an effective method to quantify the coverage of surface intermediates during an electrocatalytic reaction.

Water at charged interfaces

Abstract: The ubiquity of aqueous solutions in contact with charged surfaces and the realization that the molecular-level details of water–surface interactions often determine interfacial functions and properties relevant in many natural processes have led to intensive research. Even so, many open questions remain regarding the molecular picture of the interfacial organization and preferential alignment of water molecules, as well as the structure of water molecules and ion distributions at different charged interfaces. While water, solutes and charge are present in each of these systems, the substrate can range from living tissues to metals. This diversity in substrates has led to different communities considering each of these types of aqueous interface. In this Review, by considering water in contact with metals, oxides and biomembranes, we show the essential similarity of these disparate systems. While in each case the classical mean-field theories can explain many macroscopic and mesoscopic observations, it soon becomes apparent that such theories fail to explain phenomena for which molecular properties are relevant, such as interfacial chemical conversion. We highlight the current knowledge and limitations in our understanding and end with a view towards future opportunities in the field. What do a rock in a river, a red blood cell in our body and the electrodes inside a car battery have in common? Charged surfaces in contact with water. Although a unified approach to study such a variety of systems is not available yet, the current understanding — even with its limitations — paves the road to the development of new concepts and techniques.

Operando Investigation of Ag-Decorated Cu2O Nanocube Catalysts with Enhanced CO2 Electroreduction toward Liquid Products

Abstract: Direct conversion of carbon dioxide into multicarbon liquid fuels by the CO2 electrochemical reduction reaction (CO2 RR) can contribute to the decarbonization of the global economy. Here, well-defined Cu2 O nanocubes (NCs, 35 nm) uniformly covered with Ag nanoparticles (5 nm) were synthesized. When compared to bare Cu2 O NCs, the catalyst with 5 at % Ag on Cu2 O NCs displayed a two-fold increase in the Faradaic efficiency for C2+ liquid products (30 % at -1.0 VRHE ), including ethanol, 1-propanol, and acetaldehyde, while formate and hydrogen were suppressed. Operando X-ray absorption spectroscopy revealed the partial reduction of Cu2 O during CO2 RR, accompanied by a reaction-driven redispersion of Ag on the CuOx NCs. Data from operando surface-enhanced Raman spectroscopy further uncovered significant variations in the CO binding to Cu, which were assigned to Ag-Cu sites formed during CO2 RR that appear crucial for the C-C coupling and the enhanced yield of liquid products.

Is direct seawater splitting economically meaningful

Abstract: Electrocatalytic water splitting is the key process for the formation of green fuels for energy transport and storage in a sustainable energy economy. Besides electricity, it requires water, an aspect that seldomly has been considered until recently. As freshwater is a limited resource (<1% of earth's water), lately, plentiful reports were published on direct seawater (around 96.5% of earth's water) splitting without or with additives (buffers or bases). Alternatively, the seawater can be split in two steps, where it is first purified by reverse osmosis and then split in a conventional water electrolyser. This quantitative analysis discusses the challenges of the direct usage of non-purified seawater. Further, herein, we compare the energy requirements and costs of seawater purification with those of conventional water splitting. We find that direct seawater splitting has substantial drawbacks compared to conventional water splitting and bears almost no advantage. In short, it is less promising than the two-step scenario, as the capital and operating costs of water purification are insignificant compared to those of electrolysis of pure water.

Potential‐dependent Morphology of Copper Catalysts During CO2 Electroreduction Revealed by In Situ Atomic Force Microscopy

Abstract: Electrochemical AFM is a powerful tool for the real-space characterization of catalysts under realistic electrochemical CO2 reduction (CO2 RR) conditions. The evolution of structural features ranging from the micrometer to the atomic scale could be resolved during CO2 RR. Using Cu(100) as model surface, distinct nanoscale surface morphologies and their potential-dependent transformations from granular to smoothly curved mound-pit surfaces or structures with rectangular terraces are revealed during CO2 RR in 0.1 m KHCO3 . The density of undercoordinated copper sites during CO2 RR is shown to increase with decreasing potential. In situ atomic-scale imaging reveals specific adsorption occurring at distinct cathodic potentials impacting the observed catalyst structure. These results show the complex interrelation of the morphology, structure, defect density, applied potential, and electrolyte in copper CO2 RR catalysts.

Roadmap on organic–inorganic hybrid perovskite semiconductors and devices

Abstract: Metal halide perovskites are the first solution processed semiconductors that can compete in their functionality with conventional semiconductors, such as silicon. Over the past several years, perovskite semiconductors have reported breakthroughs in various optoelectronic devices, such as solar cells, photodetectors, light emitting and memory devices, and so on. Until now, perovskite semiconductors face challenges regarding their stability, reproducibility, and toxicity. In this Roadmap, we combine the expertise of chemistry, physics, and device engineering from leading experts in the perovskite research community to focus on the fundamental material properties, the fabrication methods, characterization and photophysical properties, perovskite devices, and current challenges in this field. We develop a comprehensive overview of the current state-of-the-art and offer readers an informed perspective of where this field is heading and what challenges we have to overcome to get to successful commercialization.

Hydrogen-doped viscoplastic liquid metal microparticles for stretchable printed metal lines.

Abstract: Conductive and stretchable electrodes that can be printed directly on a stretchable substrate have drawn extensive attention for wearable electronics and electronic skins. Printable inks that contain liquid metal are strong candidates for these applications, but the insulating oxide skin that forms around the liquid metal particles limits their conductivity. This study reveals that hydrogen doping introduced by ultrasonication in the presence of aliphatic polymers makes the oxide skin highly conductive and deformable. X-ray photoelectron spectroscopy and atom probe tomography confirmed the hydrogen doping, and first-principles calculations were used to rationalize the obtained conductivity. The printed circuit lines show a metallic conductivity (25,000 S cm–1), excellent electromechanical decoupling at a 500% uniaxial stretching, mechanical resistance to scratches and long-term stability in wide ranges of temperature and humidity. The self-passivation of the printed lines allows the direct printing of three-dimensional circuit lines and double-layer planar coils that are used as stretchable inductive strain sensors. Hydrogen doping and polymer adsorption at the oxide surface of liquid metal microparticles increase the conductivity and viscoplastic behaviour of the oxide, leading to liquid-metal-based printed circuits with stable resistance up to 500% strain.

Selectivity Control of Cu Nanocrystals in a Gas-Fed Flow Cell through CO2 Pulsed Electroreduction.

Abstract: In this study, we have taken advantage of a pulsed CO2 electroreduction reaction (CO2RR) approach to tune the product distribution at industrially relevant current densities in a gas-fed flow cell. We compared the CO2RR selectivity of Cu catalysts subjected to either potentiostatic conditions (fixed applied potential of -0.7 VRHE) or pulsed electrolysis conditions (1 s pulses at oxidative potentials ranging from Ean = 0.6 to 1.5 VRHE, followed by 1 s pulses at -0.7 VRHE) and identified the main parameters responsible for the enhanced product selectivity observed in the latter case. Herein, two distinct regimes were observed: (i) for Ean = 0.9 VRHE we obtained 10% enhanced C2 product selectivity (FEC2H4 = 43.6% and FEC2H5OH = 19.8%) in comparison to the potentiostatic CO2RR at -0.7 VRHE (FEC2H4 = 40.9% and FEC2H5OH = 11%), (ii) while for Ean = 1.2 VRHE, high CH4 selectivity (FECH4 = 48.3% vs 0.1% at constant -0.7 VRHE) was observed. Operando spectroscopy (XAS, SERS) and ex situ microscopy (SEM and TEM) measurements revealed that these differences in catalyst selectivity can be ascribed to structural modifications and local pH effects. The morphological reconstruction of the catalyst observed after pulsed electrolysis with Ean = 0.9 VRHE, including the presence of highly defective interfaces and grain boundaries, was found to play a key role in the enhancement of the C2 product formation. In turn, pulsed electrolysis with Ean = 1.2 VRHE caused the consumption of OH- species near the catalyst surface, leading to an OH-poor environment favorable for CH4 production.

Synergy between Metallic and Oxidized Pt Sites Unravelled during Room Temperature CO Oxidation on Pt/Ceria

Abstract: Pt-based materials are widely used as heterogeneous catalysts, in particular for pollutant removal applications. The nature of the active Pt phase responsible for CO oxidation has long been investigated with a view at designing more efficient formulations. The state of Pt has often been proposed to differ depending on experimental conditions, e.g. metallic Pt poisoned with CO being present at lower temperature before light-off, while an oxidized Pt surface prevails above light-off temperature. In stark contrast with all previous reports, we show here that both metallic and oxidized Pt are present in similar proportions under reaction conditions at the surface of ca. 1 nm nanoparticles showing high activity at 30 °C. The simultaneous presence of metallic and oxidized Pt enables a synergy between these phases. The main role of metallic Pt phase is to provide strong adsorption sites for CO, while that of oxidized Pt supposedly supplies reactive oxygen. Our results emphasize the complex dual oxidic-metallic nature of supported Pt catalysts and its evolving nature under reaction conditions, warranting a whole rethink of the mechanism of other reaction and metals, particularly redox and electrochemical reactions.

Potentially Confusing: Potentials in Electrochemistry

Abstract: A potential quantifies the capacity of a system to do work. A simple example is from mechanics: by lifting a weight, its potential energy increases. When the weight is dropped, that potential energy is converted into kinetic energy. Applying the concept of potential to electrochemical systems can be surprisingly confusing. Table 1 shows some “potentials” used in electrochemistry and their different units. To start, let us consider a voltage measured with a voltmeter for a given system. Analog voltmeters operate by passing a small current through a calibrated resistor and wire coil, generating a small magnetic field, and thus deflecting a needle attached to a fixed magnet. The current passed through the resistor, which causes needle deflection, is proportional to the voltage. This voltage, however, is not the electric potential difference of the system. Electric potential φ is the line integral of the electric field E⃗ along a path from a reference point (often at infinite distance from the system) to a given position:

Identifying structure-selectivity correlations in the electrochemical reduction of CO2: comparison of well-ordered atomically-clean and chemically-etched Cu single crystal surfaces.

Abstract: The identification of the active sites for the electrochemical reduction of CO2 (CO2 RR) to specific chemical products is elusive, owing in part to insufficient data gathered on clean and atomically well-ordered electrode surfaces. Here, ultrahigh vacuum based preparation methods and surface science characterization techniques are used with gas chromatography to demonstrate that subtle changes in the preparation of well-oriented Cu(100) and Cu(111) single-crystal surfaces drastically affect their CO2 RR selectivity. Copper single crystals with clean, flat, and atomically ordered surfaces are predicted to yield hydrocarbons; however, these were found experimentally to favor the production of H2 . Only when roughness and defects are introduced, for example by electrochemical etching or a plasma treatment, are significant amounts of hydrocarbons generated. These results show that structural and morphological effects are the key factors determining the catalytic selectivity of CO2 RR.

Direct measurement of key exciton properties: Energy, dynamics, and spatial distribution of the wave function

Abstract: 1 Fritz-Haber-Institut derMax-Planck-Gesellschaft, Berlin, Germany 2 Laboratoire de Spectroscopie Ultrarapide and Lausanne Centre for Ultrafast Science (LACUS), École polytechnique fédérale de Lausanne, ISIC, Lausanne, Switzerland 3 Institut für Theoretische Physik, Nichtlineare Optik undQuantenelektronik, Technische Universität Berlin, Berlin, Germany 4 Max Planck Institute for the Structure andDynamics ofMatter and Center for Free Electron Laser Science, Hamburg, Germany 5 Département de Physique and Fribourg Center for Nanomaterials, Université de Fribourg, Fribourg, Switzerland 6 Department of Applied Physics, KTHRoyal Institute of Technology, Stockholm, Sweden 7 SwissFEL, Paul Scherrer Institute, Villigen, Switzerland 8 Department of Physics, Chalmers University of Technology, Gothenburg, Sweden

Surface electron-hole rich species active in the electrocatalytic water oxidation

Abstract: Iridium and ruthenium and their oxides/hydroxides are the best candidates for the oxygen evolution reaction under harsh acidic conditions owing to the low overpotentials observed for Ru- and Ir-based anodes and the high corrosion resistance of Ir-oxides. Herein, by means of cutting edge operando surface and bulk sensitive X-ray spectroscopy techniques, specifically designed electrode nanofabrication and ab initio DFT calculations, we were able to reveal the electronic structure of the active IrOx centers (i.e., oxidation state) during electrocatalytic oxidation of water in the surface and bulk of high-performance Ir-based catalysts. We found the oxygen evolution reaction is controlled by the formation of empty Ir 5d states in the surface ascribed to the formation of formally IrV species leading to the appearance of electron-deficient oxygen species bound to single iridium atoms (μ1-O and μ1-OH) that are responsible for water activation and oxidation. Oxygen bound to three iridium centers (μ3-O) remains the dominant species in the bulk but do not participate directly in the electrocatalytic reaction, suggesting bulk oxidation is limited. In addition a high coverage of a μ1-OO (peroxo) species during the OER is excluded. Moreover, we provide the first photoelectron spectroscopic evidence in bulk electrolyte that the higher surface-to-bulk ratio in thinner electrodes enhances the material usage involving the precipitation of a significant part of the electrode surface and near-surface active species.

Active discovery of organic semiconductors.

Abstract: The versatility of organic molecules generates a rich design space for organic semiconductors (OSCs) considered for electronics applications. Offering unparalleled promise for materials discovery, the vastness of this design space also dictates efficient search strategies. Here, we present an active machine learning (AML) approach that explores an unlimited search space through consecutive application of molecular morphing operations. Evaluating the suitability of OSC candidates on the basis of charge injection and mobility descriptors, the approach successively queries predictive-quality first-principles calculations to build a refining surrogate model. The AML approach is optimized in a truncated test space, providing deep methodological insight by visualizing it as a chemical space network. Significantly outperforming a conventional computational funnel, the optimized AML approach rapidly identifies well-known and hitherto unknown molecular OSC candidates with superior charge conduction properties. Most importantly, it constantly finds further candidates with highest efficiency while continuing its exploration of the endless design space.

Demonstration of reduced neoclassical energy transport in Wendelstein 7-X

Abstract: Research on magnetic confinement of high-temperature plasmas has the ultimate goal of harnessing nuclear fusion for the production of electricity. Although the tokamak1 is the leading toroidal magnetic-confinement concept, it is not without shortcomings and the fusion community has therefore also pursued alternative concepts such as the stellarator. Unlike axisymmetric tokamaks, stellarators possess a three-dimensional (3D) magnetic field geometry. The availability of this additional dimension opens up an extensive configuration space for computational optimization of both the field geometry itself and the current-carrying coils that produce it. Such an optimization was undertaken in designing Wendelstein 7-X (W7-X)2, a large helical-axis advanced stellarator (HELIAS), which began operation in 2015 at Greifswald, Germany. A major drawback of 3D magnetic field geometry, however, is that it introduces a strong temperature dependence into the stellarator’s non-turbulent ‘neoclassical’ energy transport. Indeed, such energy losses will become prohibitive in high-temperature reactor plasmas unless a strong reduction of the geometrical factor associated with this transport can be achieved; such a reduction was therefore a principal goal of the design of W7-X. In spite of the modest heating power currently available, W7-X has already been able to achieve high-temperature plasma conditions during its 2017 and 2018 experimental campaigns, producing record values of the fusion triple product for such stellarator plasmas3,4. The triple product of plasma density, ion temperature and energy confinement time is used in fusion research as a figure of merit, as it must attain a certain threshold value before net-energy-producing operation of a reactor becomes possible1,5. Here we demonstrate that such record values provide evidence for reduced neoclassical energy transport in W7-X, as the plasma profiles that produced these results could not have been obtained in stellarators lacking a comparably high level of neoclassical optimization. Previously documented record values of the fusion triple product in the stellarator Wendelstein 7-X are shown to be evidence for reduced neoclassical energy transport in this optimized device.

Adsorption Enthalpies for Catalysis Modeling through Machine-Learned Descriptors.

Abstract: Heterogeneous catalysts are rather complex materials that come in many classes (e.g., metals, oxides, carbides) and shapes. At the same time, the interaction of the catalyst surface with even a relatively simple gas-phase environment such as syngas (CO and H2) may already produce a wide variety of reaction intermediates ranging from atoms to complex molecules. The starting point for creating predictive maps of, e.g., surface coverages or chemical activities of potential catalyst materials is the reliable prediction of adsorption enthalpies of all of these intermediates. For simple systems, direct density functional theory (DFT) calculations are currently the method of choice. However, a wider exploration of complex materials and reaction networks generally requires enthalpy predictions at lower computational cost.The use of machine learning (ML) and related techniques to make accurate and low-cost predictions of quantum-mechanical calculations has gained increasing attention lately. The employed approaches span from physically motivated models over hybrid physics-ΔML approaches to complete black-box methods such as deep neural networks. In recent works we have explored the possibilities for using a compressed sensing method (Sure Independence Screening and Sparsifying Operator, SISSO) to identify sparse (low-dimensional) descriptors for the prediction of adsorption enthalpies at various active-site motifs of metals and oxides. We start from a set of physically motivated primary features such as atomic acid/base properties, coordination numbers, or band moments and let the data and the compressed sensing method find the best algebraic combination of these features. Here we take this work as a starting point to categorize and compare recent ML-based approaches with a particular focus on model sparsity, data efficiency, and the level of physical insight that one can obtain from the model.Looking ahead, while many works to date have focused only on the mere prediction of databases of, e.g., adsorption enthalpies, there is also an emerging interest in our field to start using ML predictions to answer fundamental science questions about the functioning of heterogeneous catalysts or perhaps even to design better catalysts than we know today. This task is significantly simplified in works that make use of scaling-relation-based models (volcano curves), where the model outcome is determined by only one or two adsorption enthalpies and which consequently become the sole target for ML-based high-throughput screening or design. However, the availability of cheap ML energetics also allows going beyond scaling relations. On the basis of our own work in this direction, we will discuss the additional physical insight that can be achieved by integrating ML-based predictions with traditional catalysis modeling techniques from thermal and electrocatalysis, such as the computational hydrogen electrode and microkinetic modeling, as well as the challenges that lie ahead.

Tuning of dipolar interactions and evaporative cooling in a three-dimensional molecular quantum gas

Abstract: Ultracold polar molecules possess long-range, anisotropic and tunable dipolar interactions, providing opportunities to probe quantum phenomena that are inaccessible with existing cold gas platforms. However, experimental progress has been hindered by the dominance of two-body loss over elastic interactions, which prevents efficient evaporative cooling. Although recent work has demonstrated controlled interactions by confining molecules to a two-dimensional geometry, a general approach for tuning molecular interactions in a three-dimensional stable system has been lacking. Here we demonstrate tunable elastic dipolar interactions in a bulk gas of ultracold 40K87Rb molecules in three dimensions, facilitated by an electric field-induced shielding resonance that suppresses the reactive loss by a factor of 30. This improvement in the ratio of elastic to inelastic collisions enables direct thermalization. The thermalization rate depends on the angle between the collisional axis and the dipole orientation controlled by an external electric field, a direct manifestation of the anisotropic dipolar interaction. We achieve evaporative cooling mediated by the dipolar interactions in three dimensions. This work demonstrates full control of a long-lived bulk quantum gas system with tunable long-range interactions, paving the way for the study of collective quantum many-body physics. Realizing the potential of dipolar molecular gases to explore quantum physics needs elastic, tunable interactions and low temperatures. This is now possible due to advances in control that suppress molecular losses and enable efficient cooling.

Regulating oxygen activity of perovskites to promote NOx oxidation and reduction kinetics

Abstract: Understanding the adsorption and oxidation of NO on metal oxides is of immense interest to environmental and atmospheric (bio)chemistry. Here, we show that the surface oxygen activity, defined as the oxygen 2p-band centre relative to the Fermi level, dictates the adsorption and surface coverage of NOx and the kinetics of NO oxidation for La1−xSrxCoO3 perovskites. Density functional theory and ambient-pressure X-ray photoelectron spectroscopy revealed favourable NO adsorption on surface oxygen sites. Increasing the surface oxygen activity by increasing the strontium substitution led to stronger adsorption and greater storage of NO2, which resulted in more adsorbed nitrogen-like species and molecular nitrogen formed upon exposure to CO. The NO oxidation kinetics exhibited a volcano trend with surface oxygen activity, centred at La0.8Sr0.2CoO3 and with an intrinsic activity comparable to state-of-the-art catalysts. We rationalize the volcano trend by showing that increasing the NO adsorption enhances the oxidation kinetics, although NO adsorption that is too strong poisons the surface oxygen sites with adsorbed NO2 to impede the kinetics. Understanding the mechanism for the catalytic conversion of NOx is crucial to develop superior greenhouse gas abatement schemes, although it remains challenging. Here, the authors reveal important aspects of the redox properties of NOx on a La1–xSrxCoO3 perovskite by a combination of density functional theory calculations and ambient-pressure X-ray photoelectron spectroscopy.

Ultrafast dynamical Lifshitz transition

Abstract: Fermi surface is at the heart of our understanding of metals and strongly correlated many-body systems. An abrupt change in the Fermi surface topology, also called Lifshitz transition, can lead to the emergence of fascinating phenomena like colossal magnetoresistance and superconductivity. While Lifshitz transitions have been demonstrated for a broad range of materials by equilibrium tuning of macroscopic parameters such as strain, doping, pressure, and temperature, a nonequilibrium dynamical route toward ultrafast modification of the Fermi surface topology has not been experimentally demonstrated. Combining time-resolved multidimensional photoemission spectroscopy with state-of-the-art TDDFT+U simulations, we introduce a scheme for driving an ultrafast Lifshitz transition in the correlated type-II Weyl semimetal Td-MoTe2. We demonstrate that this nonequilibrium topological electronic transition finds its microscopic origin in the dynamical modification of the effective electronic correlations. These results shed light on a previously unexplored ultrafast scheme for controlling the Fermi surface topology in correlated quantum materials.

Polysulfates Block SARS-CoV-2 Uptake through Electrostatic Interactions*.

Abstract: Here we report that negatively charged polysulfates can bind to the spike protein of SARS-CoV-2 via electrostatic interactions. Using a plaque reduction assay, we compare inhibition of SARS-CoV-2 by heparin, pentosan sulfate, linear polyglycerol sulfate (LPGS) and hyperbranched polyglycerol sulfate (HPGS). Highly sulfated LPGS is the optimal inhibitor, with a half-maximal inhibitory concentration (IC 50 ) of 67 µg/mL (approx. 1.6 µM). This synthetic polysulfate exhibits more than 60-fold higher virus inhibitory activity than heparin (IC 50 : 4084 µg/mL), along with much lower anticoagulant activity. Furthermore, in molecular dynamics simulations, we verified that LPGS can bind stronger to the spike protein than heparin, and that LPGS can interact even more with the spike protein of the new N501Y and E484K variants. Our study demonstrates that the entry of SARS-CoV-2 into host cells can be blocked via electrostatic interactions, therefore LPGS can serve as a blueprint for the design of novel viral inhibitors of SARS-CoV-2.

Dynamic transformation of cubic copper catalysts during CO2 electroreduction and its impact on catalytic selectivity.

Abstract: To rationally design effective and stable catalysts for energy conversion applications, we need to understand how they transform under reaction conditions and reveal their underlying structure-property relationships. This is especially important for catalysts used in the electroreduction of carbon dioxide where product selectivity is sensitive to catalyst structure. Here, we present real-time electrochemical liquid cell transmission electron microscopy studies showing the restructuring of copper(I) oxide cubes during reaction. Fragmentation of the solid cubes, re-deposition of new nanoparticles, catalyst detachment and catalyst aggregation are observed as a function of the applied potential and time. Using cubes with different initial sizes and loading, we further correlate this dynamic morphology with the catalytic selectivity through time-resolved scanning electron microscopy measurements and product analysis. These comparative studies reveal the impact of nanoparticle re-deposition and detachment on the catalyst reactivity, and how the increased surface metal loading created by re-deposited nanoparticles can lead to enhanced C2+ selectivity and stability. Understanding the changes that occur in catalysts during reaction are key to the rational design. Here, the authors use electrochemical transmission electron microscopy and time-resolved product analysis to unveil how cubic copper oxide catalysts evolve during electrochemical CO2 reduction, linking their structural transformations with their selectivity.

Terahertz Spin‐to‐Charge Conversion by Interfacial Skew Scattering in Metallic Bilayers

Abstract: The efficient conversion of spin to charge transport and vice versa is of major relevance for the detection and generation of spin currents in spin-based electronics. Interfaces of heterostructures are known to have a marked impact on this process. Here, terahertz (THz) emission spectroscopy is used to study ultrafast spin-to-charge-current conversion (S2C) in about 50 prototypical F|N bilayers consisting of a ferromagnetic layer F (e.g., Ni81 Fe19 , Co, or Fe) and a nonmagnetic layer N with strong (Pt) or weak (Cu and Al) spin-orbit coupling. Varying the structure of the F/N interface leads to a drastic change in the amplitude and even inversion of the polarity of the THz charge current. Remarkably, when N is a material with small spin Hall angle, a dominant interface contribution to the ultrafast charge current is found. Its magnitude amounts to as much as about 20% of that found in the F|Pt reference sample. Symmetry arguments and first-principles calculations strongly suggest that the interfacial S2C arises from skew scattering of spin-polarized electrons at interface imperfections. The results highlight the potential of skew scattering for interfacial S2C and propose a promising route to enhanced S2C by tailored interfaces at all frequencies from DC to terahertz.

Ligand-Metal Charge Transfer Induced via Adjustment of Textural Properties Controls the Performance of Single-Atom Catalysts during Photocatalytic Degradation.

Abstract: Because of their peculiar nitrogen-rich structure, carbon nitrides are convenient polydentate ligands for designing single atom-dispersed photocatalysts However, the relation between catalysts' textural properties and their photophysical-photocatalytic properties is rarely elaborated Herein, we report the preparation and characterization of a series of single-atom heterogeneous catalysts featuring highly dispersed Ag and Cu species on mesoporous graphitic C3N4 We show that adjustment of materials textural properties and therefore metal single-atom coordination mode enables ligand-to-metal charge transfer (LMCT) or ligand-to-metal-to-ligand charge transfer (LMLCT), properties that were long speculated in single-atom catalysis but never observed We employ the developed materials in the degradation of organic pollutants under irradiation with visible light Kinetic investigations under flow conditions show that single atoms of Ag and Cu decrease the number of toxic organic fragmentation products while leading to a higher selectivity toward full degradation The results correlate with the selected mode of charge transfer in the designed photocatalysts and provide a new understanding of how the local environment of a single-atom catalyst affects the surface structure and reactivity The concepts can be exploited further to rationally design and optimize other single-atom materials

Operando high-pressure investigation of size-controlled CuZn catalysts for the methanol synthesis reaction.

Abstract: Although Cu/ZnO-based catalysts have been long used for the hydrogenation of CO2 to methanol, open questions still remain regarding the role and the dynamic nature of the active sites formed at the metal-oxide interface. Here, we apply high-pressure operando spectroscopy methods to well-defined Cu and Cu0.7Zn0.3 nanoparticles supported on ZnO/Al2O3, γ-Al2O3 and SiO2 to correlate their structure, composition and catalytic performance. We obtain similar activity and methanol selectivity for Cu/ZnO/Al2O3 and CuZn/SiO2, but the methanol yield decreases with time on stream for the latter sample. Operando X-ray absorption spectroscopy data reveal the formation of reduced Zn species coexisting with ZnO on CuZn/SiO2. Near-ambient pressure X-ray photoelectron spectroscopy shows Zn surface segregation and the formation of a ZnO-rich shell on CuZn/SiO2. In this work we demonstrate the beneficial effect of Zn, even in diluted form, and highlight the influence of the oxide support and the Cu-Zn interface in the reactivity. The nature of the active species over Cu/ZnO catalysts for methanol synthesis remains elusive. Here, the authors shed light on the evolution of the nanoparticle/support interface and correlate its structural and chemical transformations with changes in the catalytic performance.

Unravelling the structural complexity of glycolipids with cryogenic infrared spectroscopy

Abstract: Glycolipids are complex glycoconjugates composed of a glycan headgroup and a lipid moiety. Their modular biosynthesis creates a vast amount of diverse and often isomeric structures, which fulfill highly specific biological functions. To date, no gold-standard analytical technique can provide a comprehensive structural elucidation of complex glycolipids, and insufficient tools for isomer distinction can lead to wrong assignments. Herein we use cryogenic gas-phase infrared spectroscopy to systematically investigate different kinds of isomerism in immunologically relevant glycolipids. We show that all structural features, including isomeric glycan headgroups, anomeric configurations and different lipid moieties, can be unambiguously resolved by diagnostic spectroscopic fingerprints in a narrow spectral range. The results allow for the characterization of isomeric glycolipid mixtures and biological applications. Glycolipids are glycoconjugates with important biological functions, but techniques for their analysis are deficient. Here, the authors report the use of cryogenic gas-phase infrared spectroscopy to investigate isomerism in a set of immunologically relevant glycolipids, and show that their structural features can be accurately resolved based on a narrow spectral fingerprint region.

Core level photoelectron spectroscopy of heterogeneous reactions at liquid–vapor interfaces: Current status, challenges, and prospects

Abstract: Liquid–vapor interfaces, particularly those between aqueous solutions and air, drive numerous important chemical and physical processes in the atmosphere and in the environment X-ray photoelectron spectroscopy is an excellent method for the investigation of these interfaces due to its surface sensitivity, elemental and chemical specificity, and the possibility to obtain information on the depth distribution of solute and solvent species in the interfacial region In this Perspective, we review the progress that was made in this field over the past decades and discuss the challenges that need to be overcome for investigations of heterogeneous reactions at liquid–vapor interfaces under close-to-realistic environmental conditions We close with an outlook on where some of the most exciting and promising developments might lie in this field

Data-efficient machine learning for molecular crystal structure prediction

Abstract: The combination of modern machine learning (ML) approaches with high-quality data from quantum mechanical (QM) calculations can yield models with an unrivalled accuracy/cost ratio. However, such methods are ultimately limited by the computational effort required to produce the reference data. In particular, reference calculations for periodic systems with many atoms can become prohibitively expensive for higher levels of theory. This trade-off is critical in the context of organic crystal structure prediction (CSP). Here, a data-efficient ML approach would be highly desirable, since screening a huge space of possible polymorphs in a narrow energy range requires the assessment of a large number of trial structures with high accuracy. In this contribution, we present tailored Δ-ML models that allow screening a wide range of crystal candidates while adequately describing the subtle interplay between intermolecular interactions such as H-bonding and many-body dispersion effects. This is achieved by enhancing a physics-based description of long-range interactions at the density functional tight binding (DFTB) level—for which an efficient implementation is available—with a short-range ML model trained on high-quality first-principles reference data. The presented workflow is broadly applicable to different molecular materials, without the need for a single periodic calculation at the reference level of theory. We show that this even allows the use of wavefunction methods in CSP.

Accessing the Anisotropic Nonthermal Phonon Populations in Black Phosphorus.

Abstract: We combine ultrafast electron diffuse scattering experiments and first-principles calculations of the coupled electron-phonon dynamics to provide a detailed momentum-resolved picture of lattice thermalization in black phosphorus. The measurements reveal the emergence of highly anisotropic nonthermal phonon populations persisting for several picoseconds after exciting the electrons with a light pulse. Ultrafast dynamics simulations based on the time-dependent Boltzmann formalism are supplemented by calculations of the structure factor, defining an approach to reproduce the experimental signatures of nonequilibrium structural dynamics. The combination of experiments and theory enables us to identify highly anisotropic electron-phonon scattering processes as the primary driving force of the nonequilibrium lattice dynamics in black phosphorus. Our approach paves the way toward unravelling and controlling microscopic energy flows in two-dimensional materials and van der Waals heterostructures, and may be extended to other nonequilibrium phenomena involving coupled electron-phonon dynamics such as superconductivity, phase transitions, or polaron physics.