Scanning electron microscopy, linear sweep voltammetry, chronoamperometry, and in situ surface-enhanced Raman spectroscopy were used to investigate the electrochemical oxygen evolution reaction (OER) ...occurring on cobalt oxide films deposited on Au and other metal substrates. All experiments were carried out in 0.1 M KOH. A remarkable finding is that the turnover frequency for the OER exhibited by ∼0.4 ML of cobalt oxide deposited on Au is 40 times higher than that of bulk cobalt oxide. The activity of small amounts of cobalt oxide deposited on Pt, Pd, Cu, and Co decreased monotonically in the order Au > Pt > Pd > Cu > Co, paralleling the decreasing electronegativity of the substrate metal. Another notable finding is that the OER turnover frequency for ∼0.4 ML of cobalt oxide deposited on Au is nearly three times higher than that for bulk Ir. Raman spectroscopy revealed that the as-deposited cobalt oxide is present as Co3O4 but undergoes progressive oxidation to CoO(OH) with increasing anodic potential. The higher OER activity of cobalt oxide deposited on Au is attributed to an increase in fraction of the Co sites present as CoIV cations, a state of cobalt believed to be essential for OER to occur. A hypothesis for how CoIV cations contribute to OER is proposed and discussed.
The electrochemical reduction of carbon dioxide is sensitive to electrolyte polarization, which causes gradients in pH and the concentration of carbon dioxide to form near the cathode surface. It is ...desirable to measure the concentration of reaction-relevant species in the immediate vicinity of the cathode because the intrinsic kinetics of carbon dioxide reduction depend on the composition of the local reaction environment. Meeting this objective has proven difficult because conventional analytical methods only sample products from the bulk electrolyte. In this study, we describe the use of differential electrochemical mass spectrometry to measure the concentration of carbon dioxide and reaction products in the immediate vicinity of the cathode surface. This capability is achieved by coating the electrocatalyst directly onto the pervaporation membrane used to transfer volatile species into the mass spectrometer, thereby enabling species to be sampled directly from the electrode–electrolyte interface. This approach has been used to investigate hydrogen evolution and carbon dioxide reduction over Ag and Cu. We find that the measured CO2 reduction activity of Ag agrees well with what is measured by gas chromatography of the effluent from an H-cell operated with the same catalyst and electrolyte. A distinct advantage of our approach is that it enables observation of the depletion of carbon dioxide near the cathode surface due to reaction with hydroxyl anions evolved at the cathode surface, something that cannot be done using conventional analytical techniques. We also demonstrate that the influence of this relatively slow chemical reaction can be minimized by evaluating electrocatalytic activity during a rapid potential sweep, thereby enabling measurement of the intrinsic kinetics. For CO2 reduction over Cu, nine products can be observed simultaneously in real time. A notable finding is that the abundance of aldehydes relative to alcohols near the cathode surface is much higher than that observed in the bulk electrolyte. It is also observed that for increasingly cathodic potentials the relative abundance of ethanol increases at the expense of propionaldehyde. These findings suggest that acetaldehyde is a precursor to ethanol and propionaldehyde and that propionaldehyde is a precursor to n-propanol.
On the basis of constraints from reported experimental observations and density functional theory simulations, we propose a mechanism for the reduction of CO2 to C2 products on copper electrodes. To ...model the effects of an applied potential bias on the reactions, calculations are carried out with a variable, fractional number of electrons on the unit cell, which is optimized so that the Fermi level matches the actual chemical potential of electrons (i.e., the applied bias); an implicit electrolyte model allows for compensation of the surface charge so that neutrality is maintained in the overall simulation cell. Our mechanism explains the presence of the seven C2 species that have been detected in the reaction, as well as other notable experimental observations. Furthermore, our results shed light on the difference in activities toward C2 products between the (100) and (111) facets of copper. We compare our methodologies and findings with those in other recent mechanistic studies of the copper-catalyzed CO2 reduction reaction.
We have carried out a periodic Kohn–Sham density functional theory investigation of the pathways by which carbon–carbon bonds could be formed during the electrochemical reduction of CO2 on Cu(100) ...using a model that includes the effects of the electrochemical potential, solvent, and electrolyte. The electrochemical potential was set by relating the applied potential to the Fermi energy and then calculating the number of electrons required by the simulation cell for that specific Fermi energy. The solvent was included as a continuum dielectric, and the electrolyte was described using a linearized Poisson–Boltzmann model. The calculated potential of zero charge for a variety of surfaces agrees with experiment to within a mean average error of 0.09 V, thereby validating the assumptions of the model. Analysis of the mechanism for C–C bond formation revealed that at low-applied potential, C–C bond formation occurs through a CO dimer. However, at high applied potentials, a large activation barrier blocks this pathway; therefore, C–C bond formation occurs through reaction of adsorbed CHO and CO. Rate parameters determined from our calculations were used to simulate the kinetics of ethene formation during the electrochemical reduction of CO over a Cu(100) surface. An excellent match was observed between previously reported measurements of the partial current for ethene formation as a function of applied voltage and the variation in the partial current for C–C bond formation predicted by our microkinetic model. The electrochemical model reported here is simple, fairly easy to implement, and involves only a small increase in computational cost over calculations neglecting the effects of the electrolyte and the applied field. Therefore, it can be used to study the effects of applied potential and electrolyte composition on the energetics of surface reactions for a wide variety of electrochemical reactions.
An in situ Raman spectroscopic investigation has been carried out to identify the composition of the active phase present on the surface of nickel electrodes used for the electrochemical evolution of ...oxygen. The electrolyte in all cases was 0.1 M KOH. A freshly polished Ni electrode oxidized upon immersion in the electrolyte and at potentials approaching the evolution of oxygen developed a layer of γ-NiOOH. Electrochemical cycling of this film transformed it into β-NiOOH, which was observed to be three times more active than γ-NiOOH. The higher activity of β-NiOOH is attributed to an unidentified Ni oxide formed at a potential above 0.52 V (vs Hg/HgO reference). We have also observed that a submonolayer of Ni oxide deposited on Au exhibits a turnover frequency (TOF) for oxygen evolution that is an order of magnitude higher than that for a freshly prepared γ-NiOOH surface and more than 2-fold higher than that for a β-NiOOH surface. By contrast, a similar film deposited on Pd exhibits a TOF that is similar to that of bulk γ-NiOOH. It is proposed that the high activity of submonolayer deposits of Ni oxide on Au is due to charge transfer from the oxide to the highly electronegative Au, leading to the possible formation of a mixed Ni/Au surface oxide.
We report the results of experimental and theoretical studies aimed at developing a detailed understanding of how pulsed electrolysis alters the production of the temporal evolution of products over ...Cu and in particular increases the formation of C2+ products. The catalyst is a Cu film sputtered onto the surface of a PTFE membrane, through which the products of CO2 reduction are sampled for analysis by differential electrochemical mass spectroscopy (DEMS). To avoid changes in the catalyst morphology, the cathode potential is set at −0.8 V vs RHE and −1.15 V vs RHE. We find that the faradaic efficiency (FE) for hydrogen evolution reaction (HER) minimizes and that for the carbon dioxide reduction reaction (CO2RR) maximizes when the durations at each potential are 10 s. Under these conditions, the FE for the HER decreases to 11%, relative to 22% for static electrolysis, at −1.15 V vs RHE, and the FE for the CO2RR increases to 89%, relative to 78% for static electrolysis. Pulsed electrolysis also increases the FE for C2+ products from 68% for static electrolysis to 81%. Temporal analysis of the products by DEMS reveals that while the variation in product concentrations near the cathode begins in synchrony at the start of pulsed electrolysis, the concentration of C2H4 increases and those of CO and H2 decrease with extended time. We attribute these trends to an increase in the ratio of adsorbed CO to H on the catalyst surface. Simulation of pulsed electrolysis also shows that during the period when the cathode is at −0.8 V vs RHE, the local concentration of CO2 in the electrolyte near the cathode builds up. This inventory then allows electrolysis during the period at −1.15 V vs RHE to occur with a higher CO2 concentration than could be achieved for static electrolysis. The net effect of alternating cathode potentials is to enhance the local concentration of CO2, which favors the progress of the CO2RR relative to the HER and in particular the formation of C2+ products.
The aim of this study was to investigate the influence of Si/Al ratio on the locations of exchangeable cations in H-MFI and on the monomolecular cracking and dehydrogenation reactions of n-butane. On ...the basis of UV–visible spectroscopic analysis of Co(II) exchanged into MFI, it was inferred that the fraction of Co(II) (and, by extension, Brønsted protons) located at channel intersections relative to straight and sinusoidal channels increases with increasing Al content. Concurrently, turnover frequencies for all monomolecular reactions, and the selectivities to dehydrogenation versus cracking and to terminal cracking versus central cracking, generally increased. The changes in selectivity with Al content are consistent with the finding that the transition-state geometry for dehydrogenation is bulky and resembles a product state, and should therefore exhibit a stronger preference to occur at channel intersections relative to cracking. Increases in turnover frequencies are attributed partly to increases in intrinsic activation entropies that compensate for concurrent increases in intrinsic activation energies, most strongly for dehydrogenation and terminal cracking, resulting in increased selectivity to these reactions at higher Al content. This interpretation contrasts with the view that intrinsic activation barriers are constant. It is also observed that isobutene inhibits the rate of n-butane dehydrogenation. Theoretical calculations indicate that this effect originates from adsorption of isobutene at the channel intersections. Because cracking reaction rates are not affected by the presence of isobutene, this result suggests that the preference of dehydrogenation to occur at channel intersections is much stronger than the preference for cracking to occur at these locations.
Electrolyte cation size is known to influence the electrochemical reduction of CO2 over metals; however, a satisfactory explanation for this phenomenon has not been developed. We report here that ...these effects can be attributed to a previously unrecognized consequence of cation hydrolysis occurring in the vicinity of the cathode. With increasing cation size, the pK a for cation hydrolysis decreases and is sufficiently low for hydrated K+, Rb+, and Cs+ to serve as buffering agents. Buffering lowers the pH near the cathode, leading to an increase in the local concentration of dissolved CO2. The consequences of these changes are an increase in cathode activity, a decrease in Faradaic efficiencies for H2 and CH4, and an increase in Faradaic efficiencies for CO, C2H4, and C2H5OH, in full agreement with experimental observations for CO2 reduction over Ag and Cu.
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