Atomic Insights into the Competitive Edge of Nanosheets Splitting Water.

The oxygen evolution reaction (OER) provides the protons for many electrocatalytic power-to-X processes, such as the production of green hydrogen from water or methanol from CO2. Iridium oxohydroxides (IOHs) are outstanding catalysts for this reaction because they strike a unique balance between activity and stability in acidic electrolytes. Within IOHs, this balance varies with the atomic structure. While amorphous IOHs perform best, they are least stable. The opposite is true for their crystalline counterparts. These rules-of-thumb are used to reduce the loading of scarce IOH catalysts and retain the performance. However, it is not fully understood how activity and stability are related at the atomic level, hampering rational design. Herein, we provide simple design rules (Figure 12) derived from the literature and various IOHs within this study. We chose crystalline IrOOH nanosheets as our lead material because they provide excellent catalyst utilization and a predictable structure. We found that IrOOH signals the chemical stability of crystalline IOHs while surpassing the activity of amorphous IOHs. Their dense bonding network of pyramidal trivalent oxygens (µ3Δ-O) provides structural integrity, while allowing reversible reduction to an electronically gapped state that diminishes the destructive effect of reductive potentials. The reactivity originates from coordinative unsaturated edge sites with radical character, i.e., µ1-O oxyls. By comparing to other IOHs and literature, we generalized our findings and synthesized a set of simple rules that allow prediction of stability and reactivity of IOHs from atomistic models. We hope that these rules will inspire atomic design strategies for future OER catalysts.

Data-Centric Heterogeneous Catalysis: Identifying Rules and Materials Genes of Alkane Selective Oxidation.

Artificial intelligence (AI) can accelerate catalyst design by identifying key physicochemical descriptive parameters correlated with the underlying processes triggering, favoring, or hindering the performance. In analogy to genes in biology, these parameters might be called "materials genes" of heterogeneous catalysis. However, widely used AI methods require big data, and only the smallest part of the available data meets the quality requirement for data-efficient AI. Here, we use rigorous experimental procedures, designed to consistently take into account the kinetics of the catalyst active states formation, to measure 55 physicochemical parameters as well as the reactivity of 12 catalysts toward ethane, propane, and n-butane oxidation reactions. These materials are based on vanadium or manganese redox-active elements and present diverse phase compositions, crystallinities, and catalytic behaviors. By applying the sure-independence-screening-and-sparsifying-operator symbolic-regression approach to the consistent data set, we identify nonlinear property-function relationships depending on several key parameters and reflecting the intricate interplay of processes that govern the formation of olefins and oxygenates: local transport, site isolation, surface redox activity, adsorption, and the material dynamical restructuring under reaction conditions. These processes are captured by parameters derived from N2 adsorption, X-ray photoelectron spectroscopy (XPS), and near-ambient-pressure in situ XPS. The data-centric approach indicates the most relevant characterization techniques to be used for catalyst design and provides "rules" on how the catalyst properties may be tuned in order to achieve the desired performance.

Materials genes of heterogeneous catalysis from clean experiments and artificial intelligence.

ABSTRACT: The performance in heterogeneous catalysis is an example of a complex materials function, governed by an intricate interplay of several processes (e.g., the different surface chemical reactions, and the dynamic restructuring of the catalyst material at reaction conditions). Modeling the full catalytic progression via first-principles statistical mechanics is impractical, if not impossible. Instead, we show here how a tailored artificial-intelligence approach can be applied, even to a small number of materials, to model catalysis and determine the key descriptive parameters ("materials genes") reflecting the processes that trigger, facilitate, or hinder catalyst performance. We start from a consistent experimental set of "clean data," containing nine vanadium-based oxidation catalysts. These materials were synthesized, fully characterized, and tested according to standardized protocols. By applying the symbolic-regression SISSO approach, we identify correlations between the few most relevant materials properties and their reactivity. This approach highlights the underlying physicochemical processes, and accelerates catalyst design. IMPACT STATEMENT: Artificial intelligence (AI) accepts that there are relationships or correlations that cannot be expressed in terms of a closed mathematical form or an easy-to-do numerical simulation. For the function of materials, for example, catalysis, AI may well capture the behavior better than the theory of the past. However, currently the flexibility of AI comes together with a lack of interpretability, and AI can only predict aspects that were included in the training. The approach proposed and demonstrated in this IMPACT article is interpretable. It combines detailed experimental data (called "clean data") and symbolic regression for the identification of the key descriptive parameters (called "materials genes") that are correlated with the materials function. The approach demonstrated here for the catalytic oxidation of propane will accelerate the discovery of improved or novel materials while also enhancing physical understanding. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1557/s43577-021-00165-6.

Ethanol to Acetaldehyde Conversion under Thermal and Microwave Heating of ZnO-CuO-SiO2 Modified with WC Nanoparticles.

The nonoxidative conversion of ethanol to acetaldehyde under thermal and microwave heating was studied on mixed oxide ZnO-CuO-SiO2 catalysts modified with additives of tungsten carbide nanoparticles. The results revealed that the WC-modified catalyst exhibited superior activity and selectivity under microwave heating conditions. It is assumed that when microwave heating is used, hot zones can appear at the contact points of WC nanoparticles and active centers of the mixed oxide ZnO-CuO-SiO2 catalyst, which intensively absorb microwave energy, allowing the more efficient formation of acetaldehyde at moderate temperatures. Thermodynamic calculations of equilibrium concentrations of reagents and products allowed us to identify the optimal conditions for effective acetaldehyde production. The initial catalyst and the catalyst prepared by the coprecipitation of the oxides with the addition of WC were characterized by physicochemical methods (TPR-H2, XRD, DRIFTS of adsorbed CO). The active centers of the oxide catalyst can be Cu+ cations.

Al2 Pt for Oxygen Evolution in Water Splitting: A Strategy for Creating Multifunctionality in Electrocatalysis.

The production of hydrogen via water electrolysis is feasible only if effective and stable catalysts for the oxygen evolution reaction (OER) are available. Intermetallic compounds with well-defined crystal and electronic structures as well as particular chemical bonding features are suggested here to act as precursors for new composite materials with attractive catalytic properties. Al2 Pt combines a characteristic inorganic crystal structure (anti-fluorite type) and a strongly polar chemical bonding with the advantage of elemental platinum in terms of stability against dissolution under OER conditions. We describe here the unforeseen performance of a surface nanocomposite architecture resulting from the self-organized transformation of the bulk intermetallic precursor Al2 Pt in OER.

Ni Single Atom Catalysts for CO2 Activation.

We report on the activation of CO2 on Ni single-atom catalysts. These catalysts were synthesized using a solid solution approach by controlled substitution of 1-10 atom % of Mg2+ by Ni2+ inside the MgO structure. The Ni atoms are preferentially located on the surface of the MgO and, as predicted by hybrid-functional calculations, favor low-coordinated sites. The isolated Ni atoms are active for CO2 conversion through the reverse water-gas shift (rWGS) but are unable to conduct its further hydrogenation to CH4 (or MeOH), for which Ni clusters are needed. The CO formation rates correlate linearly with the concentration of Ni on the surface evidenced by XPS and microcalorimetry. The calculations show that the substitution of Mg atoms by Ni atoms on the surface of the oxide structure reduces the strength of the CO2 binding at low-coordinated sites and also promotes H2 dissociation. Astonishingly, the single-atom catalysts stayed stable over 100 h on stream, after which no clusters or particle formation could be detected. Upon catalysis, a surface carbonate adsorbate-layer was formed, of which the decompositions appear to be directly linked to the aggregation of Ni. This study on atomically dispersed Ni species brings new fundamental understanding of Ni active sites for reactions involving CO2 and clearly evidence the limits of single-atom catalysis for complex reactions.

Cu-based catalyst resulting from a Cu,Zn,Al hydrotalcite-like compound: a microstructural, thermoanalytical, and in situ XAS study.

A Cu-based methanol synthesis catalyst was obtained from a phase pure Cu,Zn,Al hydrotalcite-like precursor, which was prepared by co-precipitation. This sample was intrinsically more active than a conventionally prepared Cu/ZnO/Al2O3 catalyst. Upon thermal decomposition in air, the [(Cu0.5Zn0.17Al0.33)(OH)2(CO3)0.17]⋅mH2O precursor is transferred into a carbonate-modified, amorphous mixed oxide. The calcined catalyst can be described as well-dispersed "CuO" within ZnAl2 O4 still containing stabilizing carbonate with a strong interaction of Cu(2+) ions with the Zn-Al matrix. The reduction of this material was carefully analyzed by complementary temperature-programmed reduction (TPR) and near-edge X-ray absorption fine structure (NEXAFS) measurements. The results fully describe the reduction mechanism with a kinetic model that can be used to predict the oxidation state of Cu at given reduction conditions. The reaction proceeds in two steps through a kinetically stabilized Cu(I) intermediate. With reduction, a nanostructured catalyst evolves with metallic Cu particles dispersed in a ZnAl2 O4 spinel-like matrix. Due to the strong interaction of Cu and the oxide matrix, the small Cu particles (7 nm) of this catalyst are partially embedded leading to lower absolute activity in comparison with a catalyst comprised of less-embedded particles. Interestingly, the exposed Cu surface area exhibits a superior intrinsic activity, which is related to a positive effect of the interface contact of Cu and its surroundings.

Estimation of phase distortions of the photoplethysmographic signal in digital IIR filtering.

Pre-processing of the photoplethysmography (PPG) signal plays an important role in the analysis of the pulse wave signal. The task of pre-processing is to remove noise from the PPG signal, as well as to transmit the signal without any distortions for further analysis. The integrity of the pulse waveform is essential since many cardiovascular parameters are calculated from it using morphological analysis. Digital filters with infinite impulse response (IIR) are widely used in the processing of PPG signals. However, such filters tend to change the pulse waveform. The aim of this work is to quantify the PPG signal distortions that occur during IIR filtering in order to select a most suitable filter and its parameters. To do this, we collected raw finger PPG signals from 20 healthy volunteers and processed them by 5 main digital IIR filters (Butterworth, Bessel, Elliptic, Chebyshev type I and type II) with varying parameters. The upper cutoff frequency varied from 2 to 10 Hz and the filter order-from 2nd to 6th. To assess distortions of the pulse waveform, we used the following indices: skewness signal quality index (SSQI), reflection index (RI) and ejection time compensated (ETc). It was found that a decrease in the upper cutoff frequency leads to damping of the dicrotic notch and a phase shift of the pulse wave signal. The minimal distortions of a PPG signal are observed when using Butterworth, Bessel and Elliptic filters of the 2nd order. Therefore, we can recommend these filters for use in applications aimed at morphological analysis of finger PPG waveforms of healthy subjects.

Influence of the Structure of Hydrothermal-Synthesized TiO2 Nanowires Formed by Annealing on the Photocatalytic Reduction of CO2 in H2O Vapor.

The present study investigates the photocatalytic properties of hydrothermally synthesized TiO2 nanowires (NWs) for CO2 reduction in H2O vapor. It has been demonstrated that TiO2 NWs, thermally treated at 500-700 °C, demonstrate an almost tenfold higher yield of products compared to the known commercial powder TiO2 P25. It has been found that the best material is a combination of anatase, TiO2-B and rutile. The product yield increases with increasing heat treatment temperature of TiO2 NWs. This is associated with an increase in the degree of crystallinity of the material. It is shown that the best product yield of the CO2 reduction in H2O vapor is achieved when the TiO2 NW photocatalyst is heated to 100 °C.

The Composite TiO2-CuOx Layers Formed by Electrophoretic Method for CO2 Gas Photoreduction.

This study demonstrates the ability to control the properties of TiO2-CuOx composite layers for photocatalytic applications by using a simple electrophoretic deposition method from isopropanol-based suspension. To obtain uniform layers with a controlled composition, the surfactant sodium lauryl sulfate was used, which influenced the electrophoretic mobility of the particles and the morphology of the deposited layers. The TiO2-CuOx composite layers with different CuOx contents (1.5, 5.5, and 11 wt.%) were obtained. It is shown that the optical band gap measured by UV-VIS-NIR diffuse reflectance spectra. When CuOx is added to TiO2, two absorption edges corresponding to TiO2 and CuOx are observed, indicating a broadening of the photosensitivity range of the material relative to pure TiO2. An open-circuit potential study shows that by changing the amount of CuOx in the composite material, one can control the ratio of free charge carriers (n and p) and, therefore, the catalytic properties of the material. As a result, the TiO2-CuOx composite layers have enhanced photocatalytic activity compared to the pure TiO2 layer: methanol yield grows with increasing CuOx content during CO2 photoreduction.

Interference Phenomena and Stimulated Emission in ZnO Films on Sapphire.

We studied the texturing, roughness, and morphology features of ZnO films grown on the R (11¯02)-, M (101¯0)-, A (112¯0)-, and C (0001)-planes of sapphire, as well as their optical and luminescent properties. We showed that the growth conditions, substrate orientation, and the presence of a buffer layer significantly affected the structure and morphology of the growing films, which was reflected in their optical and radiative properties. In particular, films grown on the A- and M- planes of sapphire showed the highest UV radiation brightness values and exhibited stimulated emissions upon pulsed photoexcitation. The dependence of the topography of the film surface on the substrate orientation allowed the formation of a smooth continuous film with pronounced interference properties using the R- and M- planes of sapphire. A change in the crystallographic orientation, as well as a significant enhancement in crystallinity and luminescence, were observed for ZnO films grown on R-plane sapphire substrates with a gold buffer layer as compared to films grown on bare substrates. At the same time, the use of gold facilitates a significant smoothing of the film's surface, retaining its interference properties. The sensitivity of interference and laser properties to changes in the external environment, as well as the ease of fabrication of such structures, create prospects for their application as key elements of optical converters, chemical and biological sensors, and sources of coherent radiation.

Excitonic Mechanisms of Stimulated Emission in Low-Threshold ZnO Microrod Lasers with Whispering Gallery Modes.

Whispering gallery mode (WGM) ZnO microlasers gain attention due to their high Q-factors and ability to provide low-threshold near-UV lasing. However, a detailed understanding of the optical gain mechanisms in such structures has not yet been achieved. In this work, we study the mechanisms of stimulated emission (SE) in hexagonal ZnO microrods, demonstrating high-performance WGM lasing with thresholds down to 10-20 kW/cm2 and Q-factors up to ~3500. The observed SE with a maximum in the range of 3.11-3.17 eV at room temperature exhibits a characteristic redshift upon increasing photoexcitation intensity, which is often attributed to direct recombination in the inverted electron-hole plasma (EHP). We show that the main contribution to room-temperature SE in the microrods studied, at least for near-threshold excitation intensities, is made by inelastic exciton-electron scattering rather than EHP. The shape and perfection of crystals play an important role in the excitation of this emission. At lower temperatures, two competing gain mechanisms take place: exciton-electron scattering and two-phonon assisted exciton recombination. The latter forms emission with a maximum in the region near ~3.17 eV at room temperature without a significant spectral shift, which was observed only from weakly faceted ZnO microcrystals in this study.

Morphology and Luminescence of Flexible Free-Standing ZnO/Zn Composite Films Grown by Vapor Transport Synthesis.

A method for fabricating flexible free-standing ZnO/Zn composite films from the vapor phase using a regular array of silicon microwhiskers as a substrate is presented. The structural and morphological peculiarities, as well as luminescent properties of the films, were studied. The films have a hybrid structure consisting of two main microlayers. The first layer is formed directly on the tops of Si whiskers and has a thickness up to 10 µm. This layer features a polycrystalline structure and well-developed surface morphology. The second layer, which makes up the front side of the films, is up to 100 µm thick and consists of large microcrystals. The films show good bending strength-in particular, resistance to repeated bending and twisting-which is provided by a zinc metallic part constituting the flexible carrier of the films. ZnO photoluminescence was observed from both surfaces of the films but with conspicuous spectral differences. In particular, a significant weakening of ZnO green luminescence (more than 10 times) at an almost constant intensity of UV near-band edge emission was found for the polycrystalline side of the films as compared to the microcrystalline side. A high degree of homogeneity of the luminescent properties of the films over their area was demonstrated. The results obtained emphasize the relevance of further studies of such ZnO structures-in particular, for application in flexible devices, sensors, photocatalysis and light generation.

The Influence of the Chemical Potential on Defects and Function of Perovskites in Catalysis.

A Sm-deficient Sm0.96MnO3 perovskite was prepared on a gram scale to investigate the influence of the chemical potential of the gas phase on the defect concentration, the oxidation states of the metals and the nature of the oxygen species at the surface. The oxide was treated at 450°C in nitrogen, synthetic air, oxygen, water vapor or CO and investigated for its properties as a catalyst in the oxidative dehydrogenation of propane both before and after treatment. After treatment in water vapor, but especially after treatment with CO, increased selectivity to propene was observed, but only when water vapor was added to the reaction gas. As shown by XRD, SEM, EDX and XRF, the bulk structure of the oxide remained stable under all conditions. In contrast, the surface underwent strong changes. This was shown by AP-XPS and AP-NEXAFS measurements in the presence of the different gas atmospheres at elevated temperatures. The treatment with CO caused a partial reduction of the metals at the surface, leading to changes in the charge of the cations, which was compensated by an increased concentration of oxygen defects. Based on the present experiments, the influence of defects and concentration of electrophilic oxygen species at the catalyst surface on the selectivity in propane oxidation is discussed.

Ultraviolet Luminescence of ZnO Whiskers, Nanowalls, Multipods, and Ceramics as Potential Materials for Fast Scintillators.

The presented work is dedicated to the study and comparison of scintillating properties of zinc oxide samples prepared in different morphologies: whiskers, nanowalls, multipods, and ceramics. It was shown that total transmittance, photo- and radioluminescence spectra, and radioluminescence kinetics can vary significantly depending on sample structure and preparation conditions. The highest total transmittance was registered for ZnO ceramics (>50% at 0.5 mm thickness). Differences in the transmittance of whiskers, nanowalls, and multipods can be attributed to their shape and thickness which affects the amount of light refraction and scattering. The study of radioluminescence demonstrated that all samples, except undoped ceramics and air annealed whiskers, have predominantly fast luminescence with a decay time <1 ns. High transmittance of ceramics opens the way for their use in the registration of high energy X-ray and gamma radiation, where a large volume of scintillators is required. In cases, where large scintillator thickness is not a necessity, one may prefer to use other ZnO structures, such as ensembles of whiskers and nanowalls. Studies of near-band-edge luminescence components at low temperatures showed that the structure is quite similar in all samples except Ga doped ceramics.

Microwave-Assisted Synthesis of Stable and Highly Active Ir Oxohydroxides for Electrochemical Oxidation of Water.

Water splitting for hydrogen production in acidic media has been limited by the poor stability of the anodic electrocatalyst devoted to the oxygen evolution reaction (OER). To help circumvent this problem we have synthesized a class of novel Ir oxohydroxides by rapid microwave-asisted hydrothermal synthesis, which bridges the gap between electrodeposited amorphous IrOx films and crystalline IrO2 electrocatalysts prepared by calcination routes. For electrode loadings two orders of magnitude below current standards, the synthesized compounds present an unrivalled combination of high activity and stability under commercially relevant OER conditions in comparison to reported benchmarks, without need for pretreatment. The best compound achieved a lifetime 33 times longer than the best commercial Ir benchmark. Thus, the reported efficient synthesis of an Ir oxohydroxide phase with superior intrinsic OER performance constitutes a major step towards the targeted design of cost-efficient Ir based OER electrocatalysts for acidic media.

High-Performance Supported Iridium Oxohydroxide Water Oxidation Electrocatalysts.

The synthesis of a highly active and yet stable electrocatalyst for the anodic oxygen evolution reaction (OER) remains a major challenge for acidic water splitting on an industrial scale. To address this challenge, we obtained an outstanding high-performance OER catalyst by loading Ir on conductive antimony-doped tin oxide (ATO)-nanoparticles by a microwave (MW)-assisted hydrothermal route. The obtained Ir phase was identified by using XRD as amorphous (XRD-amorphous), highly hydrated IrIII/IV oxohydroxide. To identify chemical and structural features responsible for the high activity and exceptional stability under acidic OER conditions with loadings as low as 20 µgIr cm-2 , we used stepwise thermal treatment to gradually alter the XRD-amorphous Ir phase by dehydroxylation and crystallization of IrO2 . This resulted in dramatic depletion of OER performance, indicating that the outstanding electrocatalytic properties of the MW-produced IrIII/IV oxohydroxide are prominently linked to the nature of the produced Ir phase. This finding is in contrast with the often reported stable but poor OER performance of crystalline IrO2 -based compounds produced through more classical calcination routes. Our investigation demonstrates the immense potential of Ir oxohydroxide-based OER electrocatalysts for stable high-current water electrolysis under acidic conditions.