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We examined the electric double-layer (EDL) of a Au(111) electrode in a dilute perchloric acid solution using a combination of capacitance measurements and in situ scanning tunnelling microscopy under electrochemical conditions (ECSTM). The "camel-shaped" capacitance curve of the EDL is studied with different cations and anions, including their impact on the potential of zero charge (PZC). We show that the ECSTM images of thermally reconstructed and of the potential-induced surface reconstruction of Au(111) in perchloric acid electrolyte resemble previous work in sulphuric acid, displaying a herringbone pattern for a thermally reconstructed surface. Once the reconstruction is lifted, the Au(111) forms islands with an average of 1 atomic step height. When the potential is lowered below that of the PZC, the potential-induced surface reconstruction results in a more disoriented pattern than the thermally reconstructed surface. ECSTM images at different potentials are correlated with the voltammogram to understand the time and potential dependence of the surface. This correlation has led to the development of a potential window technique that can be used to reveal the surface structure of Au(111) based on observing the changes in PZC in the voltammogram. This method provides an indirect approach to understanding the surface structure without always relying on ECSTM. From the voltammogram, we also observed that anions (SO42-, CH3SO3-, ClO4-, F-) interact more strongly with the Au(111) surface than the alkali cations. The cation capacitance peak shape does not depend strongly on the identity of the alkali metal cation (Li+, Na+, K+). However, the anion capacitance peak depends strongly on the anion identity. It suggests that some level of specific adsorption cannot be excluded, even for anions that are traditionally not considered to adsorb specifically (perchlorate, fluoride).
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Accurate determination of the temperature dynamics at the electrode surface is crucial for advancing electrocatalysis, particularly in the development of stable materials that aid energy conversion and storage technologies. Here, lanthanide-based in situ luminescence thermometry was used to probe local heat effects at the platinum electrode surface during alkaline water electrolysis. It is demonstrated that the oxygen evolution reaction (OER) induces a more significant temperature increase compared to the hydrogen evolution reaction (HER) under the same electrochemical conditions. This difference is attributed to variations in overpotential heating and local effects on Joule heating. Furthermore, local heat effects are not observed at increased electrolyte concentrations during the HER, whereas substantial temperature variations (up to 2 K) are detected for the OER at higher electrolyte concentrations. Our observations highlight the potential of in situ luminescence thermometry to measure interfacial temperature effects during electrocatalytic reactions.
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The addition of tetrabutylammonium (TBA+) to alkaline electrolytes enhances the hydrogen evolution reaction (HER) activity on Pt single-crystal electrodes. The concentration of TBA+ significantly influences the HER on Pt(111). Concentrations of ≤1 mM yield no significant effect on HER currents or the coverage of adsorbed hydrogen (H*) but exhibit an interaction with the OHads on the surface. Conversely, concentrations of >1 mM result in an apparent site-blocking effect for underpotential-deposited H* caused by the physisorption of the organic cation, which counterintuitively leads to an increase in the HER activity. The physisorption of TBA+ is linked to its accumulation in the diffuse layer, as it can be reversibly removed by the addition of nonadsorbing cations such as sodium. Following the previous literature on the TBA+ interaction with electrode surfaces, we ascribe this effect to the formation of a two-dimensional TBA+ film in the double layer. On stepped Pt single-crystal surfaces, TBA+ enhances HER activity at all concentrations, primarily at step sites. Our findings not only highlight the complexities of TBA+ accumulation on Pt electrodes but also offer important molecular-level insights for optimizing the HER by organic film formation on various atomic-level electrode structures.
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The Pt(100) single-crystal electrode shows four voltammetric features in acid electrolytes, but the precise corresponding surface phenomena remain unresolved. Herein, a deconvolution of the classical "hydrogen region" from the "hydroxyl and anion region" is attempted by the comparison of voltammetric behavior of Pt(100) and GMLPt(100) electrodes. A systematic study performed on Pt(s)-[n(100) × (111)] and Pt(s)-[n(100) × (110)] electrodes reveals that the feature at EPI = 0.30 VRHE corresponds to pure hydrogen adsorption taking place at (111) step sites vicinal to (100) domains, while the peak at EPII = 0.36 VRHE actually involves hydroxyl replacing hydrogen at (100) domains. An analysis examined for H2SO4, HClO4, CH3SO3H, and HF demonstrates that the specific (H)SO4- adsorption commences at EPIII = 0.40 VRHE and effectively suppresses the formation of hydroxyl at the (100) terrace at higher potentials 0.40 < EPIV < 0.75 VRHE. Non-specifically adsorbing anions (ClO4-, CH3SO3- and F-) would only interact with the hydroxyl phase formed on the Pt(100) terrace in both potential regions.
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Kinetic and nonkinetic contributions to the Tafel slope value can be separated using a Tafel slope plot, where a constant Tafel slope region indicates kinetic meaningfulness. Here, we compare the Tafel slope values obtained from linear sweep voltammetry to the values obtained from chronoamperometry and impedance spectroscopy, and we apply the Tafel slope plot to various electrocatalytic reactions. We show that similar Tafel slope values are observed from the different techniques under high-mass-transport conditions for the oxygen evolution reaction on NiFeOOH in 0.2 M KOH. However, for the alkaline hydrogen evolution reaction and the CO2 reduction reaction, no horizontal Tafel slope regions were observed. In contrast, we obtained the expected Tafel slope of 30 mV/dec for the HER on Pt in 1 M HClO4. We argue that widespread application of the Tafel slope plot, or similar numerical differentiation techniques, would result in an improved comparison of kinetic data for many electrocatalytic reactions when the traditional Tafel plot analysis is ambiguous.
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Electrochemical CO2 reduction on Ni has recently been shown to have the unique ability to produce longer hydrocarbon chains in small but measurable amounts. However, the effects of the many parameters of this reaction remain to be studied in more detail. Here, we have investigated the effect of temperature, bulk CO2 concentration, potential, the reactant, cations, and anions on the formation of hydrocarbons via a chain growth mechanism on Ni. We show that temperature increases the activity but also the formation of coke, which deactivates the catalyst. The selectivity and thus the chain growth probability is mainly affected by the potential and the electrolyte composition. Remarkably, CO reduction shows lower activity but a higher chain growth probability than CO2 reduction. We conclude that hydrogenation is likely to be the rate-determining step and hypothesize that this could happen either by *CO hydrogenation or by termination of the hydrocarbon chain. These insights open the way to further development and optimization of Ni for electrochemical CO2 reduction.
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The evolution of electrogenerated gas bubbles during water electrolysis can significantly hamper the overall process efficiency. Promoting the departure of electrochemically generated bubbles during (water) electrolysis is therefore beneficial. For a single bubble, a departure from the electrode surface occurs when buoyancy wins over the downward-acting forces (e.g., contact, Marangoni, and electric forces). In this work, the dynamics of a pair of H2 bubbles produced during the hydrogen evolution reaction in 0.5 M H2SO4 using a dual platinum microelectrode system is systematically studied by varying the electrode distance and the cathodic potential. By combining high-speed imaging and electrochemical analysis, we demonstrate the importance of bubble-bubble interactions in the departure process. We show that bubble coalescence may lead to substantially earlier bubble departure as compared to buoyancy effects alone, resulting in considerably higher reaction rates at a constant potential. However, due to continued mass input and conservation of momentum, repeated coalescence events with bubbles close to the electrode may drive departed bubbles back to the surface beyond a critical current, which increases with the electrode spacing. The latter leads to the resumption of bubble growth near the electrode surface, followed by buoyancy-driven departure. While less favorable at small electrode spacing, this configuration proves to be very beneficial at larger separations, increasing the mean current up to 2.4 times compared to a single electrode under the conditions explored in this study.
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The exact mechanism behind the cation-assisted hydrogen oxidation reaction (HOR) on platinum electrodes in alkaline media remains disputed. We show that the cation effects at platinum display a remarkable structure sensitivity: not only the H adsorption but also the HOR activity on (111) terrace sites are independent of the nature of cation and cation concentration. On (110) step sites, at low cation concentration and mildly alkaline media, cations promote the HOR, whereas at more alkaline pH and consequently higher near-surface cation concentrations, the HOR is inhibition by the cations. Moreover, the role of the cation on terrace-OHad is different from that on step-OHad, as can also be observed from the inhibition of the HOR current by terrace-OHad at higher potentials. These results suggest that near the onset potential, HOR mainly takes place on steps, but under diffusion-limited conditions at higher overpotential, HOR mainly takes place on terraces.
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The kinetics of hydrogen evolution reaction (HER) in alkaline media, a reaction central to alkaline water electrolyzers, is not accurately captured by traditional adsorption-based activity descriptors. As a result, the exact mechanism and the main driving force for the water reduction or HER rate remain hotly debated. Here, we perform extensive kinetic measurements on the pH- and cation-dependent HER rate on Pt single-crystal electrodes in alkaline conditions. We find that cations interacting with Pt step sites control the HER activity, while they interact only weakly with Pt(111) and Pt(100) terraces and, therefore, cations do not affect HER kinetics on terrace sites. This is reflected by divergent activity trends as a function of pH as well as cation concentration on stepped Pt surfaces vs Pt surfaces that do not feature steps, such as Pt(111). We show that HER activity can be optimized by rationally tuning these step-cation interactions via selective adatom deposition at the steps and by choosing an optimal electrolyte composition. Our work shows that the catalyst and the electrolyte must be tailored in conjunction to achieve the highest possible HER activity.
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The efficiency of electrolysis is reduced due to the sluggish oxygen evolution reaction (OER). Besides catalyst properties, electrocatalytic activity also depends on the interaction of the electrocatalyst with the electrolyte. Here, we show that the addition of small amounts of Li+ to Fe-free NaOH or KOH electrolytes activates NiFeOOH for the OER compared to single-cation electrolytes. Moreover, the activation was maintained when the solution was returned to pure NaOH. Importantly, we show that the origin of activation by Li+ cations is primarily non-kinetic in nature, as the OER onset for the mixed electrolyte does not change and the Tafel slope at low current density is ~30â mV/dec in both electrolytes. However, the increase of the apparent Tafel slope remains lower at increasing current densities in the presence of Li+. Based on electrochemical quartz crystal microbalance and in situ X-ray absorption spectroscopy measurements, we show that this reduction of non-kinetic effects is due to enhanced intercalation of sodium, water and hydroxide. This enhanced electrolyte penetration facilitates the OER, especially at higher current densities and for increased catalyst loading. Our work shows that mixed electrolytes where distinct cations can have different roles provide a simple and promising strategy towards improved OER rates.
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A considerable carbon loss of CO2 electroreduction in neutral and alkaline media severely limits its industrial viability as a result of the homogeneous reaction of CO2 and OH- under interfacial alkalinity. Here, to mitigate homogeneous reactions, we conducted CO2 electroreduction in mildly acidic media. By modulating the interfacial reaction environment via multiple electrolyte effects, the parasitic hydrogen evolution reaction is suppressed, leading to a faradaic efficiency of over 80% for CO on the planar Au electrode. Using the rotating ring-disk electrode technique, the Au ring constitutes an in situ CO collector and pH sensor, enabling the recording of the Faradaic efficiency and monitoring of interfacial reaction environment while CO2 reduction takes place on the Au disk. The dominant branch of hydrogen evolution reaction switches from the proton reduction to the water reduction as the interfacial environment changes from acidic to alkaline. By comparison, CO2 reduction starts within the proton reduction region as the interfacial environment approaches near-neutral conditions. Thereafter, proton reduction decays, while CO2 reduction takes place, as the protons are increasingly consumed by the OH- electrogenerated from CO2 reduction. CO2 reduction reaches its maximum Faradaic efficiency just before water reduction initiates. Slowing the mass transport lowers the proton reduction current, while CO2 reduction is hardly influenced. In contrast, appropriate protic anion, e.g., HSO4- in our case, and weakly hydrated cations, e.g., K+, accelerate CO2 reduction, with the former providing extra proton flux but higher local pH, and the latter stabilizing the *CO2- intermediate.
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Heterogeneous catalysts are widely used to promote chemical reactions. Although it is known that chemical reactions usually happen on catalyst surfaces, only specific surface sites have high catalytic activity. Thus, identifying active sites and maximizing their presence lies at the heart of catalysis research1-4, in which the classic model is to categorize active sites in terms of distinct surface motifs, such as terraces and steps1,5-10. However, such a simple categorization often leads to orders of magnitude errors in catalyst activity predictions and qualitative uncertainties of active sites7,8,11,12, thus limiting opportunities for catalyst design. Here, using stepped Pt(111) surfaces and the electrochemical oxygen reduction reaction (ORR) as examples, we demonstrate that the root cause of larger errors and uncertainties is a simplified categorization that overlooks atomic site-specific reactivity driven by surface stress release. Specifically, surface stress release at steps introduces inhomogeneous strain fields, with up to 5.5% compression, leading to distinct electronic structures and reactivity for terrace atoms with identical local coordination, and resulting in atomic site-specific enhancement of ORR activity. For the terrace atoms flanking both sides of the step edge, the enhancement is up to 50 times higher than that of the atoms in the middle of the terrace, which permits control of ORR reactivity by either varying terrace widths or controlling external stress. Thus, the discovery of the above synergy provides a new perspective for both fundamental understanding of catalytically active atomic sites and design principles of heterogeneous catalysts.
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Palladium is one of the most important catalysts due to its widespread use in heterogeneous catalysis and electrochemistry. However, an understanding of the electrochemical processes and interfacial phenomena at Pd single-crystal electrodes/electrolytes is still scarce. In this work, the electrochemical behavior of the Pd(111) electrode was studied by the combination of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in different acidic electrolytes, namely, sulfuric acid, perchlorate acid, methane sulfonic acid, and hydrofluoric acid. An analysis of CV profiles shows the strong adsorption of all anions at low electrode potential, partially overlapping with underpotential deposited hydrogen (UPD-H), leading to the appearance of a pair of sharp peaks in what would be considered the "hydrogen region". All anions studied (HSO4-, ClO4-, CH3SO3-, and F-) adsorb specifically and interact with (or effectively block) the surface-adsorbed hydroxyl phase formed on the Pd(111) terrace at higher potentials. Strikingly, the scan rate-dependent results show that the process of anion adsorption and desorption is a kinetically rather slow step. EIS measurements show that the exact mechanism of this slow anion ad/desorption process actually stems from (sub)surface phenomena: the direct hydrogen insertion into Pd lattice (hydrogen subsurface absorption) commences from ca. 0.40 V and leads to the formation of (subsurface) Pd hydrides (PdHx). We argue that the subsurface hydrogen phase significantly alters the work function and thereby the kinetics of the anion adsorption and desorption processes, leading to irreversible peaks in the voltammetry. This precise understanding is important in guiding further fundamental work on Pd single crystals and will be crucial to advancing the eventual design of optimized Pd electrocatalysts.
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Online techniques for the quantitative analysis of reaction products have many advantages over offline methods. However, owing to the low product formation rates in electrochemical reactions, few of these techniques can be coupled to electrochemistry. An exception is differential electrochemical mass spectrometry (DEMS), which gains increasing popularity not least because of its high time resolution in the sub-second regime. DEMS is often combined with a dual thin-layer cell (a two-compartment flow cell), which helps to mitigate a number of problems that arise due to the existence of a vacuum|electrolyte interface. However, the efficiency with which this cell transfers volatile reaction products into the vacuum of the mass spectrometer is far below 100%. Therefore, a calibration constant that considers not only the sensitivity of the DEMS setup but also the transfer efficiency of the dual thin-layer cell is needed to translate the signals observed in the mass spectrometer into electrochemical product formation rates. However, it can be challenging or impossible to design an experiment that yields such a calibration constant. Here, we show that the transfer efficiency of the dual thin-layer cell depends on the diffusion coefficient of the analyte. Based on this observation, we suggest a two-point calibration method. That is, a plot of the logarithm of the transfer efficiencies determined for H2 and O2 versus the logarithm of their diffusion coefficients defines a straight line. Extrapolation of this line to the diffusion coefficient of another analyte yields a good estimate of its transfer efficiency. This is a versatile and easy calibration method, because the transfer efficiencies of H2 and O2 are readily accessible for a large range of electrode-electrolyte combinations.
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Understanding and manipulating gas bubble evolution during electrochemical water splitting is a crucial strategy for optimizing the electrode/electrolyte/gas bubble interface. Here gas bubble dynamics are investigated during the hydrogen evolution reaction on a well-defined platinum microelectrode by varying the electrolyte composition. We find that the microbubble coalescence efficiency follows the Hofmeister series of anions in the electrolyte. This dependency yields very different types of H2 gas bubble evolution in different electrolytes, ranging from periodic detachment of a single H2 gas bubble in sulfuric acid to aperiodic detachment of small H2 gas bubbles in perchloric acid. Our results indicate that the solutal Marangoni convection, induced by the anion concentration gradient developing during the reaction, plays a critical role at practical current density conditions. The resulting Marangoni force on the H2 gas bubble and the bubble departure diameter therefore depend on how surface tension varies with concentration for different electrolytes. This insight provides new avenues for controlling bubble dynamics during electrochemical gas bubble formation.
RESUMEN
The electrochemical reduction of CO2 (CO2RR) is a sustainable alternative for producing fuels and chemicals, although the production of highly desired hydrocarbons is still a challenge due to the higher overpotential requirement in combination with the competitive hydrogen evolution reaction (HER). Tailoring the electrolyte composition is a possible strategy to favor the CO2RR over the HER. In this work we studied the solvent effect on the CO2RR on a nanostructured Cu electrode in acetonitrile solvent with different amounts of water. Similar to what has been observed for aqueous media, our online gas chromatography results showed that CO2RR in acetonitrile solvent is also structure-dependent, since nanocube-covered copper (CuNC) was the only surface (in comparison to polycrystalline Cu) capable of producing a detectable amount of ethylene (10% FE), provided there is enough water present in the electrolyte (>500 mM). In situ Fourier Transform Infrared (FTIR) spectroscopy showed that in acetonitrile solvent the presence of CO2 strongly inhibits HER by driving away water from the interface. CO is by far the main product of CO2RR in acetonitrile (>85% Faradaic efficiency), but adsorbed CO is not detected. This suggests that in acetonitrile media CO adsorption is inhibited compared to aqueous media. Remarkably, the addition of water to acetonitrile has little quantitative and almost no qualitative effect on the activity and selectivity of the CO2RR. This indicates that water is not strongly involved in the rate-determining step of the CO2RR in acetonitrile. Only at the highest water concentrations and at the CuNC surface, the CO coverage becomes high enough that a small amount of C2+ product is formed.
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Understanding the role of cations in the electrochemical CO2 reduction (CO2RR) process is of fundamental importance for practical application. In this work, we investigate how cations influence HCOOH and CO formation on PdMLPt(111) in pH 3 electrolytes. While only (a small amount of adsorbed) CO forms on PdMLPt(111) in the absence of metal cations, the onset potential of HCOOH and CO decreases with increasing cation concentrations. The cation effect is stronger on HCOOH formation than that on CO formation on PdMLPt(111). Density functional theory simulations indicate that cations facilitate both hydride formation and CO2 activation by polarizing the electronic density at the surface and stabilizing *CO2-. Although the upshift of the metal work function caused by high coverage of adsorbates limits hydride formation, the cation-induced electric field counterbalances this effect in the case of *H species, sustaining HCOOH production at mild negative potentials. Instead, at the high *CO coverages observed at very negative potentials, surface hydrides do not form, preventing the HCOOH route both in the absence and presence of cations. Our results open the way for a consistent evaluation of cationic electrolyte effects on both activity and selectivity in CO2RR on Pd-Pt catalysts.
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Studies focused on the mechanism of CO2 electroreduction (CO2RR) aim to open up opportunities to optimize reaction parameters toward selective synthesis of desired products. However, the reaction pathways for C3 compound syntheses, especially for minor compounds, remain incompletely understood. In this study, we investigated the formation pathway for hydroxyacetone, acetone, and 1,2-propanediol through CO(2)RR, which are minor products that required long electrolysis times to be detected. Our proposed reaction mechanism is based on a systematic investigation of the reduction of several functional groups on a Cu electrode, including aldehydes, ketones, ketonealdehydes, hydroxyls, hydroxycarbonyls, and hydroxydicarbonyls, as well as the coupling between CO and C2-dicarbonyl (glyoxal) or C2-hydroxycarbonyl (glycolaldehyde). This study allowed us to derive the fundamental principles of the reduction of functional groups on Cu electrodes. Our findings suggest that the formation of ethanol does not follow the glyoxal pathway, as previously suggested but instead likely occurs via the coupling of CH3* and CO. For the C3 compounds, our results suggest that 1,2-propanediol and acetone follow the hydroxyacetone pathway during CO2RR. Hydroxyacetone is likely formed through the coupling of CO and a C2-hydroxycarbonyl intermediate, such as a glycolaldehyde-like compound, as confirmed by adding glycolaldehyde to the CO(2)-saturated solution. This finding is consistent with CO2RR product distribution, as glycolaldehyde formation during CO2RR is limited, which, in turn, limits hydroxyacetone production. Our study contributes to a better understanding of the reaction mechanism for hydroxyacetone, acetone, and 1,2-propanediol synthesis from CO2RR and gives insights into these interesting compounds that may be formed electrochemically.
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Electrocatalytic glucose oxidation can produce high value chemicals, but selectivity needs to be improved. Here we elucidate the role of the Pt oxidation state on the activity and selectivity of electrocatalytic oxidation of glucose with a new analytical approach, using high-pressure liquid chromatography and high-pressure anion exchange chromatography. It was found that the type of oxidation, i.e. dehydrogenation of primary and secondary alcohol groups or oxygen transfer to aldehyde groups, strongly depends on the Pt oxidation state. Pt0 has a 7-fold higher activity for dehydrogenation reactions than for oxidation reactions, while PtOx is equally active for both reactions. Thus, Pt0 promotes glucose dialdehyde formation, while PtOx favors gluconate formation. The successive dehydrogenation of gluconate is achieved selectively at the primary alcohol group by Pt0 , while PtOx also promotes the dehydrogenation of secondary alcohol groups, resulting in more complex reaction mixtures.
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Copper is a unique catalyst for the electrochemical CO2 reduction reaction (CO2RR) as it can produce multi-carbon products, such as ethylene and propanol. As practical electrolyzers will likely operate at elevated temperatures, the effect of reaction temperature on the product distribution and activity of CO2RR on copper is important to elucidate. In this study, we have performed electrolysis experiments at different reaction temperatures and potentials. We show that there are two distinct temperature regimes. From 18 up to â¼48 °C, C2+ products are produced with higher Faradaic efficiency, while methane and formic acid selectivity decreases and hydrogen selectivity stays approximately constant. From 48 to 70 °C, it was found that HER dominates and the activity of CO2RR decreases. Moreover, the CO2RR products produced in this higher temperature range are mainly the C1 products, namely, CO and HCOOH. We argue that CO surface coverage, local pH, and kinetics play an important role in the lower-temperature regime, while the second regime appears most likely to be related to structural changes in the copper surface.