Although copper is widely used as an electrocatalyst for the CO2 reduction reaction, often little emphasis is placed on identifying exactly the facet distribution of the copper surface. Furthermore... Show moreAlthough copper is widely used as an electrocatalyst for the CO2 reduction reaction, often little emphasis is placed on identifying exactly the facet distribution of the copper surface. Furthermore, because of differing surface preparation methodologies, reported characaterization voltammograms (where applicable) often vary significantly between laboratories, even for surfaces of supposedly the same orientation. In this work, we describe a surface preparation methodology involving the combination of induction annealing and well-documented electrochemical steps, by which reproducible voltammetry for copper surfaces of different orientations can be obtained. Specifically, we investigated copper surfaces of the three principal orientations: {111}, {100} and {110}, and a representative polycrystalline surface. We compared these surfaces to surfaces reported in the literature prepared via either electropolishing or UHV-standard methodologies, where we find induction preparation to yield improvements in surface quality with respect to electropolished surfaces, though not quite as good as those obtained by UHV-preparation. Show less
Reducing CO2 to long-chain carbon products is attractive considering such products are typically more valuable than shorter ones. However, the best electrocatalyst for making such products from CO2... Show moreReducing CO2 to long-chain carbon products is attractive considering such products are typically more valuable than shorter ones. However, the best electrocatalyst for making such products from CO2, copper, lacks selectivity. By studying alternate C2+ producing catalysts we can increase our mechanistic understanding, which is beneficial for improving catalyst performance. Therefore, we investigate CO reduction on silver, as density functional theory (DFT) results predict it to be good at forming ethanol. To address the current disagreement between DFT and experimental results (ethanol vs. no ethanol), we investigated CO reduction at higher surface coverage (by increasing pressure) to ascertain if desorption effects can explain the discrepancy. In terms of product trends, our results agree with the DFT-proposed acetaldehyde-like intermediate, yielding ethanol and propanol as C2+ products-making the CO2 electrochemistry of silver very similar to that of copper at sufficiently high coverage. Show less
The electrochemical reduction of CO2 to CO is a promising technology for replacing production processes employing fossil fuels. Still, low energy efficiencies hinder the production of CO at... Show moreThe electrochemical reduction of CO2 to CO is a promising technology for replacing production processes employing fossil fuels. Still, low energy efficiencies hinder the production of CO at commercial scale. CO2 electrolysis has mainly been performed in neutral or alkaline media, but recent fundamental work shows that high selectivities for CO can also be achieved in acidic media. Therefore, we investigate the feasibility of CO2 electrolysis at pH 2–4 at indrustrially relevant conditions, using 10 cm2 gold gas diffusion electrodes. Operating at current densities up to 200 mA cm−2, we obtain CO faradaic efficiencies between 80–90% in sulfate electrolyte, with a 30% improvement of the overall process energy efficiency, in comparison with neutral media. Additionally, we find that weakly hydrated cations are crucial for accomplishing high reaction rates and enabling CO2 electrolysis in acidic media. This study represents a step towards the application of acidic electrolyzers for CO2 electroreduction. Show less
In the pursuit of a hydrogen economy, extensive research has been directed at developing acidic and alkaline hydrogen fuel cells. Such fuel cells often utilize platinum-based catalysts. These... Show moreIn the pursuit of a hydrogen economy, extensive research has been directed at developing acidic and alkaline hydrogen fuel cells. Such fuel cells often utilize platinum-based catalysts. These materials have been studied extensively in acidic conditions but not in alkaline ones. This focus on acidic systems creates a marked knowledge gap, since recent studies indicate that carbon-supported platinum (Pt/C) electrocatalysts degrade more rapidly in bases than in acids. Addressing this gap, the present work investigates Pt/C degradation at pH 2 and pH 12 using electrochemistry, transmission electron microscopy (TEM), and in situ X-ray absorption spectroscopy (XAS). TEM and XAS reveal accelerated Pt/C degradation at high pH levels, which results in increased Ostwald ripening, Smoluchowski agglomeration, and nanoparticle detachment. These processes are driven by platinum-catalyzed carbon corrosion and the dissolution and redeposition of platinum nanoparticles. Although these processes take place at both low and high pH levels, basic conditions accelerate the degradation. Base-enhanced Pt dissolution and redeposition was assessed in further detail, revealing an oxidation onset reduction of 100 mV in the base; however, there were no significant differences between undissolved Pt oxidation in acid and in base. The results suggest that soluble Pt oxidation products are stabilized in the base instead. These conclusions are important for translating acidbased literature to alkaline conditions. Show less
The interfacial capacitance of a metal electrode in contact with a dilute electrolyte is generally expected to follow the behavior predicted by the Gouy-Chapman-Stern model. Recent experiments ... Show moreThe interfacial capacitance of a metal electrode in contact with a dilute electrolyte is generally expected to follow the behavior predicted by the Gouy-Chapman-Stern model. Recent experiments [Angew. Chem. Int. Ed. 2020, 59, 711], however, have shown that a deviation from the Gouy-Chapman behavior is observed even in dilute electrolytes on platinum and gold single-crystal electrodes. Such deviations are usually attributed to an interaction between the surface and the electrolyte ions. However, a quantitative model showing that the strong deviations from the Gouy-Champan behavior observed for Pt can be ascribed to such an effect is still lacking, particularly as other experimental observables do not indicate a strong ion adsorption. Here, we propose a double-layer model that is capable of reproducing the main experimental findings in a simple and (in parts) analytical way. The analytical model thereby includes the attractive ion-surface interaction via an additional capacitive element connected in parallel to the Gouy-Chapman capacitance. By comparing the model predictions to experiment, we subsequently infer characteristics of the ion-surface interaction. In particular, we find that the model predicts the attractive interaction to be weak (weaker than a typical chemical bond formed when contact adsorbing) and that the interaction has to be very similar for all ions. Furthermore, for a good agreement with experiment, ion-size effects are suggested to play a role in determining the potential of minimum capacitance. Show less
The electrocatalytic reduction of carbon dioxide is widely studied for the sustainable production of fuels and chemicals. Metal ions in the electrolyte influence the reaction performance, although... Show moreThe electrocatalytic reduction of carbon dioxide is widely studied for the sustainable production of fuels and chemicals. Metal ions in the electrolyte influence the reaction performance, although their main role is under discussion. Here we studied CO2 reduction on gold electrodes through cyclic voltammetry and showed that, without a metal cation, the reaction does not take place in a pure 1 mM H2SO4 electrolyte. We further investigated the CO2 reduction with and without metal cations in solution using scanning electrochemical microscopy in the surface-generation tip-collection mode with a platinum ultramicroelectrode as a CO and H2 sensor. CO is only produced on gold, silver or copper if a metal cation is added to the electrolyte. Density functional theory simulations confirmed that partially desolvated metal cations stabilize the CO2– intermediate via a short-range electrostatic interaction, which enables its reduction. Overall, our results redefine the reaction mechanism and provide definitive evidence that positively charged species from the electrolyte are key to stabilize the crucial reaction intermediate. Show less
The ubiquity of aqueous solutions in contact with charged surfaces and the realization that the molecular-level details of water-surface interactions often determine interfacial functions and... Show moreThe ubiquity of aqueous solutions in contact with charged surfaces and the realization that the molecular-level details of water-surface interactions often determine interfacial functions and properties relevant in many natural processes have led to intensive research. Even so, many open questions remain regarding the molecular picture of the interfacial organization and preferential alignment of water molecules, as well as the structure of water molecules and ion distributions at different charged interfaces. While water, solutes and charge are present in each of these systems, the substrate can range from living tissues to metals. This diversity in substrates has led to different communities considering each of these types of aqueous interface. In this Review, by considering water in contact with metals, oxides and biomembranes, we show the essential similarity of these disparate systems. While in each case the classical mean-field theories can explain many macroscopic and mesoscopic observations, it soon becomes apparent that such theories fail to explain phenomena for which molecular properties are relevant, such as interfacial chemical conversion. We highlight the current knowledge and limitations in our understanding and end with a view towards future opportunities in the field.What do a rock in a river, a red blood cell in our body and the electrodes inside a car battery have in common? Charged surfaces in contact with water. Although a unified approach to study such a variety of systems is not available yet, the current understanding - even with its limitations - paves the road to the development of new concepts and techniques. Show less
The effect of naphthalene-based additives: naphthalene (NPT), naphthalenesulfonate (NPTS) and hydroxynaphthalenesulfonate (HNPTS) on the kinetics of tin electrodeposition on a boron-doped diamond ... Show moreThe effect of naphthalene-based additives: naphthalene (NPT), naphthalenesulfonate (NPTS) and hydroxynaphthalenesulfonate (HNPTS) on the kinetics of tin electrodeposition on a boron-doped diamond (BDD) electrode has been studied by means of chronoamperometry and scanning electron microscopy (SEM). Potentiostatic current transients in the absence and the presence of naphthalene-based additives are analyzed by using the Scharifker-Hills model. A strong decrease of the kinetics of tin nucleation on BDD was observed in the presence of naphthalene-based additives, NPT showing the smallest effect and HNPTS showing the largest effect. From the long-term Cottrell behavior of the transients, similar values of tin(II) diffusion coefficients were obtained for all additives, suggesting that there is no complexation of Sn(II) by the additives and that the charge-transfer kinetics itself is not substantially influenced by the presence of the additives. In the absence of additives, tin deposition on BDD displays a progressive nucleation and growth mechanism at the least negative potentials, switching to instantaneous nucleation and growth at more negative potential. In the presence of NPTS and HNPTS, progressive nucleation and growth transients are observed. The growth mode results are confirmed by the tin features observed in the scanning electron micrographs. In conclusion, NPT, NPTS and HNPTS mainly decrease the rate of the nucleation of tin deposition, most likely by blocking or reducing access to active nucleation sites. In comparison, ethoxylated alpha-napthalenesulfonic acid (ENSA, a commonly used additive in the tin plating industry) inhibits tin deposition process on BDD even more strongly. These observations show a striking similarity to our previous study of tin deposition on gold electrodes. Show less
Granda Marulanda, L.P.; McCrum, I.T.; Koper, M.T.M. 2021
Determining the adsorption potential of adsorbed ions in the field of computational electrocatalysis is of great interest to study their interaction with the electrode material and the solvent, and... Show moreDetermining the adsorption potential of adsorbed ions in the field of computational electrocatalysis is of great interest to study their interaction with the electrode material and the solvent, and to map out surface phase diagrams and reaction pathways. Calculating the adsorption potentials of ions with density functional theory and comparing across various ions requires an accurate reference energy of the ion in solution and electrons at the same electrochemical scale. Here we highlight a previously used method for determining the reference free energy of solution phase ions using a simple electrochemical thermodynamic cycle, which allows this free energy to be calculated from that of a neutral gas-phase or solid species and an experimentally measured equilibrium potential, avoiding the need to model solvent around the solution phase ion in the electronic structure calculations. While this method is not new, we describe its use and utility in detail and show that this same method can be used to find the free energy of any ion from any reaction, as long as the half-cell equilibrium potential is known, even for reactions that do not transfer the same number of protons and electrons. To illustrate its usability, we compare the adsorption potentials obtained with DFT of I*, Br*, Cl*, and SO4 * on Pt(111) and Au(111) and OH* and Ag* on Pt(111) with those measured experimentally and find that this simple and computationally affordable method reproduces the experimental trends. Show less
Among heterogeneous electrocatalysts, gold comes closest to the ideal reversible electrocatalysis of CO2 electrochemical reduction (CO2RR) to CO and, vice versa, of CO electroxidation to CO2 (COOR)... Show moreAmong heterogeneous electrocatalysts, gold comes closest to the ideal reversible electrocatalysis of CO2 electrochemical reduction (CO2RR) to CO and, vice versa, of CO electroxidation to CO2 (COOR). The nature of the electrolyte has proven to crucially affect the electrocatalytic behavior of gold. Herein, we expand the understanding of the effect of the widely employed bicarbonate electrolytes on CO2RR using gold monocrystalline electrodes, detecting the CO evolved during CO2RR by selective anodic oxidation. First, we show that CO2RR to CO is facet dependent and that Au(110) is the most active surface. Additionally, we detect by in situ FTIR measurements the presence of adsorbed COtop only on the Au(110) surface. Second, we highlight the importance of acid-base equilibria for both CO2RR and COOR by varying the electrolyte (partial pressure of CO2 and the concentration of the bicarbonate) and voltammetric parameters. In this way, we identify different regimes of surface pH and bicarbonate speciation, as a function of the current and electrolyte conditions. We reveal the importance of the acid-base bicarbonate/carbonate couple, not only as a buffering equilibrium but also as species involved in the electrochemical reactions under study. Show less
In this work we study the role of alkali metal cation concentration and electrolyte pH in altering the kinetics of the hydrogen evolution reaction (HER) at gold (Au) electrodes. We show that at... Show moreIn this work we study the role of alkali metal cation concentration and electrolyte pH in altering the kinetics of the hydrogen evolution reaction (HER) at gold (Au) electrodes. We show that at moderately alkaline pH (pH 11), increasing the cation concentration significantly enhances the HER activity on Au electrodes (with a reaction order approximate to 0.5). Based on these results we suggest that cations play a central role in stabilizing the transition state of the rate-determining Volmer step by favorably interacting with the dissociating water molecule (*H-OH delta--cat(+)). Moreover, we show that increasing electrolyte pH (pH 10 to pH 13) tunes the local field strength, which in turn indirectly enhances the activity of HER by tuning the near-surface cation concentration. Interestingly, a too high near-surface cation concentration (at high pH and high cation concentration) leads to a lowering of the HER activity, which we ascribe to a blockage of the surface by near-surface cations. Show less
The electrochemical reduction of CO2 aims to be a central technology to store excess electricity generated by wind and solar energy. However, the reaction is hindered by the competition with the... Show moreThe electrochemical reduction of CO2 aims to be a central technology to store excess electricity generated by wind and solar energy. However, the reaction is hindered by the competition with the hydrogen evolution reaction. In this paper, we present a detailed quantitative study of the Faradaic efficiency (FE) to CO on a gold electrode under well-defined mass-transport conditions using rotating ring-disk electrode voltammetry. Varying the concentration of the bicarbonate and the electrolyte cation employing different rotation rates, we map out how these parameters affect the FE(CO). We identify two different potential regimes for the electrolyte effects, characterized by a different dependence on the cation and bicarbonate concentrations. For hydrogen evolution, we analyze the nature of the proton donor for an increasingly negative potential, showing how it changes from carbonic acid to bicarbonate and to water. Our study gives detailed insights into the role of electrolyte composition and mass transport, and helps defining optimized electrolyte conditions for a high FE(CO). Show less
Cathodic corrosion is an enigmatic electrochemical process that etches metallic electrodes at potentials below 0 V versus the normal hydrogen electrode. Although this phenomenon was discovered in... Show moreCathodic corrosion is an enigmatic electrochemical process that etches metallic electrodes at potentials below 0 V versus the normal hydrogen electrode. Although this phenomenon was discovered in the late 1800s by Fritz Haber, it remained mostly unnoticed during the 20th century and only attracted increased attention in the past decade. This recent attention has generated marked improvements in both the fundamental knowledge and the applications of cathodic corrosion. Fundamental new insights were gained into the effects and possible reaction intermediates of cathodic corrosion. Complementing these insights, recent advances involve applications of cathodic corrosion for nanoparticle synthesis and electrocatalyst modification. Both these applied and fundamental advances will be discussed in this short review on cathodic corrosion. Show less
In this article, we investigate the poisoning reaction that occurs at platinum electrodes during the electrocatalytic hydrogenation of acetone. A better understanding of this poisoning reaction is... Show moreIn this article, we investigate the poisoning reaction that occurs at platinum electrodes during the electrocatalytic hydrogenation of acetone. A better understanding of this poisoning reaction is important to develop electrocatalysts that are both active for the hydrogenation of carbonyl compounds and resilient against poisoning side reactions. We adsorb acetone to Pt(331), Pt(911), Pt(510), and Pt(533) (i.e., Pt[2(111) x (110)], Pt[5(100) x (111)], [5(100) x (110)], and Pt[4(111) x (100), respectively])) as well as Pt(100) single-crystal electrodes and perform reductive and oxidative stripping experiments after electrolyte exchange. We found that acetone adsorbs molecularly intact on all sites apart from Pt(100) terrace sites and can be stripped reductively from the electrode surface at a potential positive of hydrogen evolution. However, at Pt(100) terraces, acetone adsorbs dissociatively as carbon monoxide, which remains attached to the electrode surface and leads to its poisoning. Strikingly, dissociative adsorption does not occur on step sites with (100) geometry, which suggests that the dissociative adsorption of acetone is limited to Pt(100) terraces featuring a certain minimum ensemble number of freely available Pt atoms. Show less
The electroreduction of CO2 (CO2RR) is a promising strategy toward sustainable fuels. Cu is the only Earth-abundant and pure metal capable of catalyzing CO2-to-hydrocarbons conversion with... Show moreThe electroreduction of CO2 (CO2RR) is a promising strategy toward sustainable fuels. Cu is the only Earth-abundant and pure metal capable of catalyzing CO2-to-hydrocarbons conversion with significant Faradaic efficiencies; yet, its dynamic structure under operando CO2RR conditions remains unknown. Here, we track the Cu structure operando by electrochemical scanning tunneling microscopy and Raman spectroscopy. Surprisingly, polycrystalline Cu surfaces reconstruct forming Cu nanocuboids whose size can be controlled by the polarization potential and the time employed in their in situ synthesis, without the assistance of organic surfactants and/or halide anions. If the Cu surface is covered by a graphene monolayer, smaller features with enhanced catalytic activity for CO2RR can be prepared. The graphene-protecting layer softens the 3D morphological changes that Cu-based catalysts suffer when exposed to aggressive electrochemical environments and allows us to track the kinetic roughening process. This novel strategy is promising for improving Cu long-term stability, and consequently, it could be used as a platform to ultimately control product selectivity. Show less
Graf, M.; Vonbun-Feldbauer, G.B.; Koper, M.T.M. 2021
Plasmonic photocatalysis via hot charge carriers suffers from their short lifetime compared with the sluggish kinetics of most reactions. To increase lifetime, adsorbates on the surface of a... Show morePlasmonic photocatalysis via hot charge carriers suffers from their short lifetime compared with the sluggish kinetics of most reactions. To increase lifetime, adsorbates on the surface of a plasmonic metal may create preferential states for electrons to be excited from. We demonstrate this effect with O adsorbates on a nanoporous gold electrode. Nanoporous gold is used to obtain a broadband optical response, to increase the obtained photocurrent, and to provide a SERS-active substrate. Only with adsorbates present, we observe significant photocurrents. Illumination also increases the adsorbate coverage above its dark potential-dependent equilibrium, as derived from a two-laser in situ SERS approach. Density functional theory calculations confirm the appearance of excitable states below the Fermi level. The photocurrent enhancement and broadband characteristics reveal the potential of the plasmonic approach to improve the efficiency of photoelectrochemical water splitting. Show less
Seawater electrolysis is an attractive approach for producing clean hydrogen fuel in scenarios where freshwater is scarce and renewable electricity is abundant. However, chloride ions (Cl-) in... Show moreSeawater electrolysis is an attractive approach for producing clean hydrogen fuel in scenarios where freshwater is scarce and renewable electricity is abundant. However, chloride ions (Cl-) in seawater can accelerate electrode corrosion and participate in the undesirable chlorine evolution reaction (CER). This problem is especially acute in acidic conditions that naturally arise at the anode as a result of the desired oxygen evolution reaction (OER). Herein, we demonstrate that ultrathin silicon oxide (SiOx) overlayers on model platinum anodes are highly effective at suppressing the CER in the presence of 0.6 M Cl- in both acidic and unbuffered pH-neutral electrolytes by blocking the transport of Cl- to the catalytically active buried interface while allowing the desired oxygen evolution reaction (OER) to occur there. The permeability of Cl- in SiOx overlayers is 3 orders of magnitude less than that of Cl- in a conventional salt-selective membrane used in reverse osmosis desalination. The overlayers also exhibit robust stability over 12 h in chronoamperometry tests at moderate overpotentials. SiOx overlayers demonstrate a promising step toward achieving selective and stable seawater electrolysis without the need to adjust the pH of the electrolyte. Show less
Bondü, C.J.; Graf, M.; Goyal, A.; Koper, M.T.M. 2020
In this article we investigate the electrochemical reduction of CO2 at gold electrodes under mildly acidic conditions. Differential electrochemical mass spectroscopy (DEMS) is used to quantify the... Show moreIn this article we investigate the electrochemical reduction of CO2 at gold electrodes under mildly acidic conditions. Differential electrochemical mass spectroscopy (DEMS) is used to quantify the amounts of formed hydrogen and carbon monoxide as well as the consumed amount of CO2. We investigate how the Faradaic efficiency of CO formation is affected by the CO2 partial pressure (0.1-0.5 bar) and the proton concentration (1-0.25 mM). Increasing the former enhances the rate of CO2 reduction and suppresses hydrogen evolution from proton reduction, leading to Faradaic efficiencies close to 100%. Hydrogen evolution is suppressed by CO2 reduction as all protons at the electrode surfaces are used to support the formation of water (CO2 + 2H(+) + 2e(-) -> CO + H2O). Under conditions of slow mass transport, this leaves no protons to support hydrogen evolution. On the basis of our results, we derive a general design principle for acid CO2 electrolyzers to suppress hydrogen evolution from proton reduction: the rate of CO/OH- formation must be high enough to match/compensate the mass transfer of protons to the electrode surface. Show less
