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

Origin of the heat induced improvement of catalytic activity and stability of MnOx electrocatalysts for water oxidation

Catalysis of the oxygen evolution reaction (OER) by earth-abundant materials in the near-neutral pH regime is of great interest as it is the key reaction for non-fossil fuel production. To address the pertinent stability problems and insufficiently understood structure–activity relations, we investigate the influence of moderate annealing (100–300 °C for 20 min) for two types of electrodeposited Mn oxide films with contrasting properties. Upon annealing, the originally inactive and structurally well-ordered Oxide 1 of birnessite type became as OER active as the non-heated Oxide 2, which has a highly disordered atomic structure. Oxide 2 also improved its activity upon heating, but more important is the stability improvement: the operation time increased by about two orders of magnitude (in 0.1 M KPi at pH 7). Aiming at atomistic understanding, electrochemical methods including quantitative analysis of impedance spectra, X-ray spectroscopy (XANES and EXAFS), and adapted optical spectroscopies (infrared, UV-vis and Raman) identified structure–reactivity relations. Oxide structures featuring both di-μ-oxo bridged Mn ions and (close to) linear mono-μ-oxo Mn3+–O–Mn4+ connectivity seem to be a prerequisite for OER activity. The latter motif likely stabilizes Mn3+ ions at higher potentials and promotes electron/hole hopping, a feature related to electrical conductivity and reflected in the strongly accelerated rates of Mn oxidation and O2 formation. Poor charge mobility, which may result from a low level of Mn3+ ions at high potentials, likely promotes inactivation after prolonged operation. Oxide structures related to the perovskite-like ζ-Mn2O3 were formed after the heating of Oxide 2 and could favour stabilization of Mn ions in oxidation states lower than +4. This rare phase was previously found only at high pressure (20 GPa) and temperature (1200 °C) and this is the first report where it was stable under ambient conditions

Geometric distortions in nickel oxy hydroxide electrocatalysts by redox inactive iron ions

The dramatic change in electrochemical behavior of nickel (oxy)hydroxide films upon incorporation of Fe ions provides an opportunity to establish effective electrocatalyst design principles. We characterize a photochemically deposited series of Fe–Ni (oxy)hydroxides by X-ray absorption spectroscopy and track the voltage- and composition-dependence of structural motifs. We observe a trigonal distortion in di-μ-hydroxo bridged NiII–NiII motifs that is preserved following a symmetric contraction of Ni–O bond lengths when oxidized to di-μ-oxo NiIV–NiIV. Incorporation of Fe ions into the structure generates di-μ-hydroxo NiII–FeIII motifs in which Ni–Fe distances are dependent on nickel oxidation state, but Fe–O bond lengths are not. This asymmetry minimizes the trigonal distortion in di-μ-hydroxo NiII–FeIII motifs and neighboring di-μ-hydroxo NiII–NiII sites in the reduced state, but exacerbates it in the oxidized state. We attribute both the Fe-induced anodic shift in nickel-based redox peaks and the improved ability to catalyze the oxygen evolution reaction to this inversion in geometric distortions. Spectroelectrochemical experiments reveal a previously unreported change in optical absorbance at ca. 1.5 V vs. RHE in Fe-containing samples. We attribute this feature to oxidation of nickel ions in di-μ-hydroxo NiII–FeIII motifs, which we propose is the process relevant to catalytic oxygen evolution

Electrocatalytic Water Oxidation at Neutral pH Deciphering the Rate Constraints for an Amorphous Cobalt Phosphate Catalyst System

The oxygen evolution reaction OER is pivotal in sustainable fuel production. Neutral pH OER reduces operational risks and enables direct coupling to electrochemical CO2 reduction, but typically is hampered by low current densities. Here, the rate limitations in neutral pH OER are clarified. Using cobalt based catalyst films and phosphate ions as essential electrolyte bases, current potential curves are recorded and simulated. Operando X ray spectroscopy shows the potential dependent structural changes independent of the electrolyte phosphate concentration. Operando Raman spectroscopy uncovers electrolyte acidification at a micrometer distance from the catalyst surface, limiting the Tafel slope regime to low current densities. The electrolyte proton transport is facilitated by diffusion of either phosphate ions base pathway or H3O ions water pathway . The water pathway is not associated with an absolute current limit but is energetically inefficient due to the Tafel slope increase by 60 mV dec amp; 8722;1, shown by an uncomplicated mathematical model. The base pathway is a specific requirement in neutral pH OER and can support high current densities, but only with accelerated buffer base diffusion. Catalyst internal phosphate diffusion or other internal transport mechanisms do not limit the current densities. A proof of principle experiment shows that current densities exceeding 1 A cm amp; 8722;2 can also be achieved in neutral pH OE

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

Reactivity Determinants in Electrodeposited Cu Foams for Electrochemical CO2 Reduction

CO2 reduction is of significant interest for the production of nonfossil fuels. The reactivity of eight Cu foams with substantially different morphologies was comprehensively investigated by analysis of the product spectrum and in situ electrochemical spectroscopies (X‐ray absorption near edge structure, extended X‐ray absorption fine structure, X‐ray photoelectron spectroscopy, and Raman spectroscopy). The approach provided new insight into the reactivity determinants: The morphology, stable Cu oxide phases, and *CO poisoning of the H2 formation reaction are not decisive; the electrochemically active surface area influences the reactivity trends; macroscopic diffusion limits the proton supply, resulting in pronounced alkalization at the CuCat surfaces (operando Raman spectroscopy). H2 and CH4 formation was suppressed by macroscopic buffer alkalization, whereas CO and C2H4 formation still proceeded through a largely pH‐independent mechanism. C2H4 was formed from two CO precursor species, namely adsorbed *CO and dissolved CO present in the foam cavities

Reactivity Determinants in Electrodeposited Cu Foams for Electrochemical CO₂ Reduction

CO2 reduction is of significant interest for the production of nonfossil fuels. The reactivity of eight Cu foams with substantially different morphologies was comprehensively investigated by analysis of the product spectrum and in situ electrochemical spectroscopies (X‐ray absorption near edge structure, extended X‐ray absorption fine structure, X‐ray photoelectron spectroscopy, and Raman spectroscopy). The approach provided new insight into the reactivity determinants: The morphology, stable Cu oxide phases, and *CO poisoning of the H2 formation reaction are not decisive; the electrochemically active surface area influences the reactivity trends; macroscopic diffusion limits the proton supply, resulting in pronounced alkalization at the CuCat surfaces (operando Raman spectroscopy). H2 and CH4 formation was suppressed by macroscopic buffer alkalization, whereas CO and C2H4 formation still proceeded through a largely pH‐independent mechanism. C2H4 was formed from two CO precursor species, namely adsorbed *CO and dissolved CO present in the foam cavities

Tuning cobalt eg occupation of Co-NCNT by manipulation of crystallinity facilitates more efficient oxygen evolution and reduction

Co encapsulated in N-doped carbon nanotubes (Co-NCNT) catalysts are of high interest as bifunctional electrocatalyst material for both efficient oxygen evolution and reduction (OER/ORR) in applications of rechargeable metal-air batteries. Up to now, the role played by the functional metal species in OER/ORR is still insufficiently understood. The main focus of our research is to shed light on the mechanistic role of the Co species that serve as active sites in the bi-functional Co-NCNT catalysts. It is found that S700 exhibits an outstanding OER/ORR activity. We thus hypothesize that CoII and CoIII clusters predominately function as active sites in the OER and ORR processes, respectively. Furthermore, OER/ORR activity for Co-NCNT catalyst primarily correlates to eg occupation. A near-unity occupancy of the eg orbital of S700 is revealed to be the cause for the maximum intrinsic OER/ORR activity, which provides guidelines for the design of highly active catalysts