Cooperative Effects Drive Water Oxidation Catalysis in Cobalt Electrocatalysts through the Destabilization of Intermediates.

A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple overlapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (∼0.34 eV/monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O2 evolution onset coincide due to weaker binding and destabilization (∼0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

Probing Degradation in Lithium Ion Batteries with On-Chip Electrochemistry Mass Spectrometry.

The rapid uptake of lithium ion batteries (LIBs) for large scale electric vehicle and energy storage applications requires a deeper understanding of the degradation mechanisms. Capacity fade is due to the complex interplay between phase transitions, electrolyte decomposition and transition metal dissolution; many of these poorly understood parasitic reactions evolve gases as a side product. Here we present an on-chip electrochemistry mass spectrometry method that enables ultra-sensitive, fully quantified and time resolved detection of volatile species evolving from an operating LIB. The technique's electrochemical performance and mass transport is described by a finite element model and then experimentally used to demonstrate the variety of new insights into LIB performance. We show the versatility of the technique, including (a) observation of oxygen evolving from a LiNiMnCoO2 cathode and (b) the solid electrolyte interphase formation reaction on graphite in a variety of electrolytes, enabling the deconvolution of lithium inventory loss (c) the first direct evidence, by virtue of the improved time resolution of our technique, that carbon dioxide reduction to ethylene takes place in a lithium ion battery. The emerging insight will guide and validate battery lifetime models, as well as inform the design of longer lasting batteries.

Dynamic Interfacial Reaction Rates from Electrochemistry-Mass Spectrometry.

Electrochemistry-mass spectrometry is a versatile and reliable tool to study the interfacial reaction rates of Faradaic processes with high temporal resolutions. However, the measured mass spectrometric signals typically do not directly correspond to the partial current density toward the analyte due to mass transport effects. Here, we introduce a mathematical framework, grounded on a mass transport model, to obtain a quantitative and truly dynamic partial current density from a measured mass spectrometer signal by means of deconvolution. Furthermore, it is shown that the time resolution of electrochemistry-mass spectrometry is limited by entropy-driven processes during mass transport to the mass spectrometer. The methodology is validated by comparing the measured impulse responses of hydrogen and oxygen evolution to the model predictions and subsequently applied to uncover dynamic phenomena during hydrogen and oxygen evolution in an acidic electrolyte.

Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte.

To date, copper is the only heterogeneous catalyst that has shown a propensity to produce valuable hydrocarbons and alcohols, such as ethylene and ethanol, from electrochemical CO2 reduction (CO2R). There are variety of factors that impact CO2R activity and selectivity, including the catalyst surface structure, morphology, composition, the choice of electrolyte ions and pH, and the electrochemical cell design. Many of these factors are often intertwined, which can complicate catalyst discovery and design efforts. Here we take a broad and historical view of these different aspects and their complex interplay in CO2R catalysis on Cu, with the purpose of providing new insights, critical evaluations, and guidance to the field with regard to research directions and best practices. First, we describe the various experimental probes and complementary theoretical methods that have been used to discern the mechanisms by which products are formed, and next we present our current understanding of the complex reaction networks for CO2R on Cu. We then analyze two key methods that have been used in attempts to alter the activity and selectivity of Cu: nanostructuring and the formation of bimetallic electrodes. Finally, we offer some perspectives on the future outlook for electrochemical CO2R.

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts.

CO electroreduction activity on oxide-derived Cu (OD-Cu) was found to correlate with metastable surface features that bind CO strongly. OD-Cu electrodes prepared by H2 reduction of Cu2O precursors reduce CO to acetate and ethanol with nearly 50% Faradaic efficiency at moderate overpotential. Temperature-programmed desorption of CO on OD-Cu revealed the presence of surface sites with strong CO binding that are distinct from the terraces and stepped sites found on polycrystalline Cu foil. After annealing at 350 °C, the surface-area corrected current density for CO reduction is 44-fold lower and the Faradaic efficiency is less than 5%. These changes are accompanied by a reduction in the proportion of strong CO binding sites. We propose that the active sites for CO reduction on OD-Cu surfaces are strong CO binding sites that are supported by grain boundaries. Uncovering these sites is a first step toward understanding the surface chemistry necessary for efficient CO electroreduction.

Unraveling the reaction mechanisms for furfural electroreduction on copper.

Electrochemical routes for the valorization of biomass-derived feedstock molecules offer sustainable pathways to produce chemicals and fuels. However, the underlying reaction mechanisms for their electrochemical conversion remain elusive. In particular, the exact role of proton-electron coupled transfer and electrocatalytic hydrogenation in the reaction mechanisms for biomass electroreduction are disputed. In this work, we study the reaction mechanism underlying the electroreduction of furfural, an important biomass-derived platform chemical, combining grand-canonical (constant-potential) density functional theory-based microkinetic simulations and pH dependent experiments on Cu under acidic conditions. Our simulations indicate the second PCET step in the reaction pathway to be the rate- and selectivity-determining step for the production of the two main products of furfural electroreduction on Cu, i.e., furfuryl alcohol and 2-methyl furan, at moderate overpotentials. We further identify the source of Cu's ability to produce both products with comparable activity in their nearly equal activation energies. Furthermore, our microkinetic simulations suggest that surface hydrogenation steps play a minor role in determining the overall activity of furfural electroreduction compared to PCET steps due to the low steady-state hydrogen coverage predicted under reaction conditions, the high activation barriers for surface hydrogenation and the observed pH dependence of the reaction. As a theoretical guideline, low pH (<1.5) and moderate potential (ca. -0.5 V vs. SHE) conditions are suggested for selective 2-MF production.

The low overpotential regime of acidic water oxidation part II: trends in metal and oxygen stability numbers.

The operating conditions of low pH and high potential at the anodes of polymer electrolyte membrane electrolysers restrict the choice of catalysts for the oxygen evolution reaction (OER) to oxides based on the rare metals iridium or ruthenium. In this work, we investigate the stability of both the metal atoms and, by quantitative and highly sensitive 18O isotope labelling experiments, the oxygen atoms in a series of RuO x and IrO x electrocatalysts during the OER in the mechanistically interesting low overpotential regime. We show that materials based on RuO x have a higher dissolution rate than the rate of incorporation of labelled oxygen from the catalyst into the O2 evolved ("labelled OER"), while for IrO x -based catalysts the two rates are comparable. On amorphous RuO x , metal dissolution and labelled OER are found to have distinct Tafel slopes. These observations together lead us to a full mechanistic picture in which dissolution and labelled OER are side processes to the main electrocatalytic cycle. We emphasize the importance of quantitative analysis and point out that since less than 0.2% of evolved oxygen contains an oxygen atom originating from the catalyst itself, lattice oxygen evolution is at most a negligible contribution to overall OER activity for RuO x and IrO x in acidic electrolyte.

The low overpotential regime of acidic water oxidation part I: the importance of O2 detection.

The high overpotential required for the oxygen evolution reaction (OER) represents a significant barrier for the production of closed-cycle renewable fuels and chemicals. Ruthenium dioxide is among the most active catalysts for OER in acid, but the activity at low overpotentials can be difficult to measure due to high capacitance. In this work, we use electrochemistry - mass spectrometry to obtain accurate OER activity measurements spanning six orders of magnitude on a model series of ruthenium-based catalysts in acidic electrolyte, quantifying electrocatalytic O2 production at potential as low as 1.30 VRHE. We show that the potential-dependent O2 production rate, i.e., the Tafel slope, exhibits three regimes, revealing a previously unobserved Tafel slope of 25 mV decade-1 below 1.4 VRHE. We fit the expanded activity data to a microkinetic model based on potential-dependent coverage of the surface intermediates from which the rate-determining step takes place. Our results demonstrate how the familiar quantities "onset potential" and "exchange current density" are influenced by the sensitivity of the detection method.