Tuning the Oxygen Reduction Reactivity of Layered Perovskites Using the Jahn-Teller Effect.

Compositional tuning of layered perovskite oxides provides a means of systematically studying how local distortions affect fundamental aspects of electrochemical reaction pathways. Structural analysis of a family of samples La1.2Sr0.8Ni1-yCoyO4 shows that Ni-rich compositions have an expanded crystalline c axis, which is anisotropically compressed by systematic Co incorporation. Raman spectra reveal the strong growth of a symmetry forbidden mode, which suggests that Co acts through localized distortions. Crystallographic and spectroscopic parameters describing this structural distortion correlate to the measured Tafel slopes for the oxygen reduction reaction for all Ni-containing samples, which is attributed to the distortion of potential energy surfaces by the Jahn-Teller expansion of d7 Ni(III) cations. Incorporation of Co not only minimizes the distortion but alters the apparent selectivity of the oxygen reduction reaction away from H2O2 and toward H2O. Rotating ring-disk electrochemical measurements, however, indicate that the apparent change in selectivity is due to activation of a first-order chemical disproportionation of H2O2 that is activated by Co in the lattice. These outcomes will support efforts to design electrocatalysts and reactors for the electrochemical synthesis of H2O2.

Raman Spectroscopic Analysis of the Reaction between Al-Si Coatings and Steel.

Hot-stamped ultrahigh strength steel components are pivotal to automotive light-weighting. Steel blanks, often coated with an aluminum-silicon (Al-Si) layer to protect them from oxidation and decarburization, are austenitized within a furnace and then simultaneously quenched and formed into shape. The Al-Si coating melts within the furnace and reacts with iron from the steel to yield an intermetallic phase that provides some long-term corrosion protection. During the intermediate liquid phase, some of the coating may transfer to the furnace components, leading to maintenance costs and operational downtime. A detailed understanding of the coating transformation mechanism is needed to avoid such production issues while ensuring that final intermetallic coatings conform to specifications. We introduce cross-sectional Raman microscopic mapping as a method to rapidly elucidate the coating transformation mechanism. Raman spectroscopic fingerprints for relevant intermetallic compounds were determined using synthesized Al-Fe-Si ternary and Al-Fe binary compounds. These fingerprints were used to map the spatial distribution of intermetallic compounds through cross sections of Al-Si-coated 22MnB5 specimens that were heated at temperatures between 570 and 900 °C. These chemical maps show that the intermetallic fraction of the coating does not grow significantly until formation of η (Al5Fe2) at the steel interface, suggesting that η facilitates extraction of iron from the steel and subsequent diffusion through the coating. Under the heating conditions used here, a series of reactions ultimately lead to a silicon-rich τ2 (Al3FeSi) phase on top of the binary η phase. The technique presented here simplifies structural analysis of intermetallic compounds, which will facilitate prototyping of strategies to optimize hot stamping.

Spherical DNA for Probing Wettability of Microplastics.

Wettability of microplastics may change due to chemical or physical transformations at their surface. In this work, we studied the adsorption of spherical nucleic acids (SNAs) with a gold nanoparticle core and linear DNA of the same sequence to probe the wettability of microplastics. Soaking microplastics in water at room temperature for 3 months resulted in the enhancement of SNA adsorption capacity and affinity, whereas linear DNA adsorption was the same on the fresh and soaked microplastics. Drying of the soaked microplastics followed by rehydration decreased the adsorption of the SNA, suggesting that the effect of soaking was reversible and related to physical changes instead of chemical changes of the microplastics. Raman spectroscopy data also revealed no chemical transformations of the soaked microplastics. Heating of microplastics over a short period induced a similar effect to long-term soaking. We propose that soaking or heating removes air entrapped in the nanosized pores at the water-plastic interface, increasing the contact surface area of the SNA to afford stronger adsorption. However, such wetted porosity would not change the adsorption of linear DNA because of its much smaller size.

Customizable Machine-Learning Models for Rapid Microplastic Identification Using Raman Microscopy.

Raman spectroscopy is commonly used in microplastics identification, but equipment variations yield inconsistent data structures that disrupt the development of communal analytical tools. We report a strategy to overcome the issue using a database of high-resolution, full-window Raman spectra. This approach enables customizable analytical tools to be easily created─a feature we demonstrate by creating machine-learning classification models using open-source random-forest, K-nearest neighbors, and multi-layer perceptron algorithms. These models yield >95% classification accuracy when trained on spectroscopic data with spectroscopic data downgraded to 1, 2, 4, or 8 cm-1 spacings in Raman shift. The accuracy can be maintained even in non-ideal conditions, such as with spectroscopic sampling rates of 1 kHz and when microplastic particles are outside the focal plane of the laser. This approach enables the creation of classification models that are robust and adaptable to varied spectrometer setups and experimental needs.

Differentiating Defects and Their Influence on Hematite Photoanodes Using X-ray Absorption Spectroscopy and Raman Microscopy.

A high degree of variability in behavior and performance of hematite as photoanodes for the oxygen evolution reaction signifies a need to improve our understanding of the interplay between defects and photoelectrochemical performance. We approach this problem by applying structure-property analysis to a series of hematite samples synthesized under either O2 or N2 environments such that they exhibit highly variable performance for photoelectrocatalytic oxygen evolution. X-ray absorption fine-structure spectroscopy and Raman spectroscopy provide parameters describing the structure of samples across the series. Systematic comparisons of these parameters to those describing photoelectrochemical performance reveal different defects in samples prepared under N2 or O2. Distinct correlations between both the iron oxidation state and charge carrier density with photoelectrocatalytic performance lead to assignment of the primary defects as oxygen vacancies (N2) and iron vacancies (O2). Differences in the structural distortions caused by these defects are seen in correlations between short-range structural parameters and photoelectrochemical behavior. These distortions are readily observed by Raman spectroscopy, suggesting that it may be possible to calibrate the width, energy, and intensity of peaks in Raman spectra to enable direct analysis of defects in hematite photoanodes.

Operando tracking of oxidation-state changes by coupling electrochemistry with time-resolved X-ray absorption spectroscopy demonstrated for water oxidation by a cobalt-based catalyst film.

Transition metal oxides are promising electrocatalysts for water oxidation, i.e., the oxygen evolution reaction (OER), which is critical in electrochemical production of non-fossil fuels. The involvement of oxidation state changes of the metal in OER electrocatalysis is increasingly recognized in the literature. Tracing these oxidation states under operation conditions could provide relevant information for performance optimization and development of durable catalysts, but further methodical developments are needed. Here, we propose a strategy to use single-energy X-ray absorption spectroscopy for monitoring metal oxidation-state changes during OER operation with millisecond time resolution. The procedure to obtain time-resolved oxidation state values, using two calibration curves, is explained in detail. We demonstrate the significance of this approach as well as possible sources of data misinterpretation. We conclude that the combination of X-ray absorption spectroscopy with electrochemical techniques allows us to investigate the kinetics of redox transitions and to distinguish the catalytic current from the redox current. Tracking of the oxidation state changes of Co ions in electrodeposited oxide films during cyclic voltammetry in neutral pH electrolyte serves as a proof of principle.

Analysis of Solid-State Reaction Mechanisms with Two-Dimensional Fourier Transform Infrared Correlation Spectroscopy.

The utility of two-dimensional generalized correlation spectroscopy (2D-COS) for tracking complex solid-state reactions is demonstrated using infrared spectra acquired during a photochemically induced decomposition reaction. Eleven different thin films, consisting of six monometallic and five bimetallic 2-ethylhexanoate complexes, were tracked as a function of photolysis time. Overlapping peaks in the infrared fingerprint region are readily discriminated using 2D-COS, enabling individual vibrational components to be used to distinguish whether carboxylate ligands are free/ionic or bound in a chelating, bridging, or monodentate fashion. This classification enables the decomposition mechanism to be tracked for all 11 samples, revealing that ligands bound in monodentate and bridging fashions are first converted to chelates before being lost as volatile products for all samples. The magnitude of the measured first-order rate constants for loss of chelated ligands is found to correlate linearly to the asymmetric stretching frequency of monodentate ligands but exhibits a V shape when plotted against the electronegativity of the metal center. We propose that loss of chelated ligands proceeds via C-O scission for highly electronegative transition metals but M-O scission for transition metals with low electronegativity. These results establish 2D-COS as a powerful tool to deconvolute and correlate individual components, enabling mechanistic analysis of complex chemical reactions.

Structural and functional role of anions in electrochemical water oxidation probed by arsenate incorporation into cobalt-oxide materials.

Direct (photo)electrochemical production of non-fossil fuels from water and CO2 requires water-oxidation catalysis at near-neutral pH in the presence of appropriate anions that serve as proton acceptors. We investigate the largely enigmatic structural role of anions in water oxidation for the prominent cobalt-phosphate catalyst (CoCat), an amorphous and hydrated oxide material. Co3([(P/As)O]4)2·8H2O served, in conjunction with phosphate-arsenate exchange, as a synthetic model system. Its structural transformation was induced by prolonged operation at catalytic potentials and probed by X-ray absorption spectroscopy not only at the metal (Co), but for the first time also at the anion (As) K-edge. For initially isostructural microcrystals, anion exchange determined the amorphization process and final structure. Comparison to amorphous electrodeposited Co oxide revealed that in CoCat, the arsenate binds not only at oxide-layer edges, but also arsenic substitutes cobalt positions within the layered-oxide structure in an unusual AsO6 coordination. Our results show that in water oxidation catalysis at near-neutral pH, anion type and exchange dynamics correlate with the catalyst structure and redox properties.

H/D Isotope Effects Reveal Factors Controlling Catalytic Activity in Co-Based Oxides for Water Oxidation.

Understanding the mechanism for electrochemical water oxidation is important for the development of more efficient catalysts for artificial photosynthesis. A basic step is the proton-coupled electron transfer, which enables accumulation of oxidizing equivalents without buildup of a charge. We find that substituting deuterium for hydrogen resulted in an 87% decrease in the catalytic activity for water oxidation on Co-based amorphous-oxide catalysts at neutral pH, while 16O-to-18O substitution lead to a 10% decrease. In situ visible and quasi-in situ X-ray absorption spectroscopy reveal that the hydrogen-to-deuterium isotopic substitution induces an equilibrium isotope effect that shifts the oxidation potentials positively by approximately 60 mV for the proton coupled CoII/III and CoIII/IV electron transfer processes. Time-resolved spectroelectrochemical measurements indicate the absence of a kinetic isotope effect, implying that the precatalytic proton-coupled electron transfer happens through a stepwise mechanism in which electron transfer is rate-determining. An observed correlation between Co oxidation states and catalytic current for both isotopic conditions indicates that the applied potential has no direct effect on the catalytic rate, which instead depends exponentially on the average Co oxidation state. These combined results provide evidence that neither proton nor electron transfer is involved in the catalytic rate-determining step. We propose a mechanism with an active species composed by two adjacent CoIV atoms and a rate-determining step that involves oxygen-oxygen bond formation and compare it with models proposed in the literature.

Identifying protons trapped in hematite photoanodes through structure-property analysis.

Uncertainty regarding the nature of structural defects in hematite and their specific impacts on material properties and photoelectrocatalytic water oxidation inhibits their development as photoanodes. We perform structure-property analysis on a series of hematite films fabricated by annealing lepidocrocite films with varied temperatures, annealing times and atmospheres and find a gradient in the magnitude of a crystal lattice distortion by tracking the relative intensity of a formally Raman inactive vibrational mode. Structure-property analysis reveals that this feature in the Raman spectrum correlates to photocurrent density, semiconductor band positions, and the onset of photoelectrocatalysis. We propose that the onset of photoelectrocatalysis is linked to the location of defects that act as intraband recombination sites; an increase in the degree of structural distortion shifts these states towards the conduction band, thereby facilitating recombination. Analysis of the nature of the key Raman vibrations, X-ray diffraction patterns, and the synthetic conditions leads us to assign the distortion to iron vacancies that are induced by the trapping of protons within the crystal lattice. The ability to rapidly diagnose a specific structural defect will aid in the optimization of fabrication protocols for hematite photoanodes.

Spectroscopic identification of active sites for the oxygen evolution reaction on iron-cobalt oxides.

The emergence of disordered metal oxides as electrocatalysts for the oxygen evolution reaction and reports of amorphization of crystalline materials during electrocatalysis reveal a need for robust structural models for this class of materials. Here we apply a combination of low-temperature X-ray absorption spectroscopy and time-resolved in situ X-ray absorption spectroelectrochemistry to analyze the structure and electrochemical properties of a series of disordered iron-cobalt oxides. We identify a composition-dependent distribution of di-µ-oxo bridged cobalt-cobalt, di-µ-oxo bridged cobalt-iron and corner-sharing cobalt structural motifs in the composition series. Comparison of the structural model with (spectro)electrochemical data reveals relationships across the composition series that enable unprecedented assignment of voltammetric redox processes to specific structural motifs. We confirm that oxygen evolution occurs at two distinct reaction sites, di-µ-oxo bridged cobalt-cobalt and di-µ-oxo bridged iron-cobalt sites, and identify direct and indirect modes-of-action for iron ions in the mixed-metal compositions.

Accounting for the Dynamic Oxidative Behavior of Nickel Anodes.

The dynamic behavior of the anodic peak for amorphous nickel oxy/hydroxide (a-NiOx) films in basic media was investigated. Chronocoulometry of films with known nickel concentrations reveals that a total of four electrons per nickel site comprise the signature anodic peak at 1.32 V during the first oxidative scan, and two electrons are passed through the associated cathodic peak on the reverse scan. The anodic and cathodic signals each contain two electrons on the successive scans. Catalytic oxygen evolution reaction (OER) was detected within the anodic peak, which is at a lower potential than is widely assumed. In order to rationalize these experimental results, we propose that the four-electron oxidation event is the conversion of the film from nickel(II) hydroxide ([Ni(II)-OH](-)) to a higher valent nickel peroxide species (e.g., Ni(IV)-OO or Ni(III)-OO·). The subsequent reduction of the nickel peroxide species is confined by a chemical step resulting in the accumulation of [Ni(II)-OOH](-), which is then oxidized by two electrons to form Ni(IV)-OO during the subsequent oxidative scan on the time scale of a cyclic voltammetric experiment. Our proposed mechanism and the experimental determination that each nickel site is oxidized by four electrons helps link the myriad of seemingly disparate literature data related to OER catalysis by nickel electrodes. The faster catalysis that occurs at higher oxidative potentials is derived from a minority species and is not elaborated here.

Water oxidation catalysis: electrocatalytic response to metal stoichiometry in amorphous metal oxide films containing iron, cobalt, and nickel.

Photochemical metal-organic deposition (PMOD) was used to prepare amorphous metal oxide films containing specific concentrations of iron, cobalt, and nickel to study how metal composition affects heterogeneous electrocatalytic water oxidation. Characterization of the films by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirmed excellent stoichiometric control of each of the 21 complex metal oxide films investigated. In studying the electrochemical oxidation of water catalyzed by the respective films, it was found that small concentrations of iron produced a significant improvement in Tafel slopes and that cobalt or nickel were critical in lowering the voltage at which catalysis commences. The best catalytic parameters of the series were obtained for the film of composition a-Fe20Ni80. An extrapolation of the electrochemical and XPS data indicates the optimal behavior of this binary film to be a manifestation of iron stabilizing nickel in a higher oxidation level. This work represents the first mechanistic study of amorphous phases of binary and ternary metal oxides for use as water oxidation catalysts, and provides the foundation for the broad exploration of other mixed-metal oxide combinations.

Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers.