pKa as a Predictive Descriptor for Electrochemical Anion Adsorption.

The adsorption of anions onto metal surfaces is important in many applications including effective (electro)catalyst design, metal surface modification, and contaminant removal in wastewater treatment. In electrocatalysis, anions can be both reactive intermediates or site-blocking spectators, where their adsorption strength therefore dictates the rate of reaction. In this work, we have measured the adsorption energy of a series of carboxylic acids on a Pt (111) single-crystal electrode surface from aqueous solution. We find that the adsorption strength of the carboxylate anion is linearly correlated with its acid-dissociation constant (pKa) and therefore the heterolytic O-H bond dissociation strength in solution. Using density functional theory modeling, we split the anion adsorption energy into a sum of the adsorption energy and electron affinity of a neutral (carboxyl) radical. Surprisingly, the adsorption energy of the carboxyl radicals are similar and therefore the large difference in electron affinity is what dictates anion adsorption strength; the greater the cost in energy to remove the electron from the anion upon adsorption, the weaker its binding. Therefore, at least within a class of anions with similar structure and surface binding atoms, both electron affinity and acidity are predictive descriptors of adsorption strength.

Site-specific reactivity of stepped Pt surfaces driven by stress release.

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.

How palladium inhibits CO poisoning during electrocatalytic formic acid oxidation and carbon dioxide reduction.

Development of reversible and stable catalysts for the electrochemical reduction of CO2 is of great interest. Here, we elucidate the atomistic details of how a palladium electrocatalyst inhibits CO poisoning during both formic acid oxidation to carbon dioxide and carbon dioxide reduction to formic acid. We compare results obtained with a platinum single-crystal electrode modified with and without a single monolayer of palladium. We combine (high-scan-rate) cyclic voltammetry with density functional theory to explain the absence of CO poisoning on the palladium-modified electrode. We show how the high formate coverage on the palladium-modified electrode protects the surface from poisoning during formic acid oxidation, and how the adsorption of CO precursor dictates the delayed poisoning during CO2 reduction. The nature of the hydrogen adsorbed on the palladium-modified electrode is considerably different from platinum, supporting a model to explain the reversibility of this reaction. Our results help in designing catalysts for which CO poisoning needs to be avoided.

A simple method to calculate solution-phase free energies of charged species in computational electrocatalysis.

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 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.

Water at charged interfaces.

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 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.

Thermodynamics of the formation of surface PtO2 stripes on Pt(111) in the absence of subsurface oxygen.

This paper examines the thermodynamics of PtO2 stripes formed as intermediates of Pt(111) surface oxidation as a function of the degree of dilation parallel to the stripes, using density functional theory and atomistic thermodynamics. Internal energy calculations predict 7/8 and 8/9 stripe structures to dominate at standard temperature and pressure, which contain 7 or 8 elevated PtO2 units per 8 or 9 supporting surface Pt atoms, respectively. Moreover, we found a thermodynamic optimum with respect to mean in-stripe Pt-Pt spacing close to that of α-PtO2. Vibrational zero point energies, including bulk layer contributions, make a small but significant contribution to the stripe free energies, leading to the 6/7 stripe being most stable, although the 7/8 structure is still close in free energy. These findings correspond closely to experimental observations, providing insight into the driving force for oxide stripe formation and structure as the initial intermediate of platinum surface oxidation, and aiding our understanding of platinum catalysts and surface roughening under oxidative conditions.

Adsorption processes on a Pd monolayer-modified Pt(111) electrode.

Specific adsorption of anions is an important aspect in surface electrochemistry for its influence on reaction kinetics in either a promoted or inhibited fashion. Perchloric acid is typically considered as an ideal electrolyte for investigating electrocatalytic reactions due to the lack of specific adsorption of the perchlorate anion on several metal electrodes. In this work, cyclic voltammetry and computational methods are combined to investigate the interfacial processes on a Pd monolayer deposited on Pt(111) single crystal electrode in perchloric acid solution. The "hydrogen region" of this PdMLPt(111) surface exhibits two voltammetric peaks: the first "hydrogen peak" at 0.246 VRHE actually involves the replacement of hydrogen by hydroxyl, and the second "hydrogen peak" HII at 0.306 VRHE appears to be the replacement of adsorbed hydroxyl by specific perchlorate adsorption. The two peaks merge into a single peak when a more strongly adsorbed anion, such as sulfate, is involved. Our density functional theory calculations qualitatively support the peak assignment and show that anions generally bind more strongly to the PdMLPt(111) surface than to Pt(111).

Hydrogen-Induced Step-Edge Roughening of Platinum Electrode Surfaces.

Electrode surfaces may change their surface structure as a result of the adsorption of chemical species, impacting their catalytic activity. Using density functional theory, we find that the strong adsorption of hydrogen at low electrode potentials promotes the thermodynamics and kinetics of a unique type of roughening of 110-type Pt step edges. This change in surface structure causes the appearance of the so-called "third hydrogen peak" in voltammograms measured on Pt electrodes, an observation that has eluded explanation for over 50 years. Understanding this roughening process is important for structure-sensitive (electro)catalysis and the development of active and stable catalysts.

BCC-Phased PdCu Alloy as a Highly Active Electrocatalyst for Hydrogen Oxidation in Alkaline Electrolytes.

Anion-exchange membrane fuel cells hold promise to greatly reduce cost by employing nonprecious metal cathode catalysts. More efficient anode catalysts are needed, however, to improve the sluggish hydrogen oxidation reaction in alkaline electrolytes. We report that BCC-phased PdCu alloy nanoparticles, synthesized via a wet-chemistry method with a critical thermal treatment, exhibit up to 20-fold HOR improvement in both mass and specific activities, compared with the FCC-phased PdCu counterparts. HOR activity of the BCC-phased PdCu is 4 times or 2 times that of Pd/C or Pt/C, respectively, in the same alkaline electrolyte. In situ HE-XRD measurements reveal that the transformation of PdCu crystalline structure favors, at low annealing temperature (<300 °C), the formation of FCC structure. At higher annealing temperatures (300-500 °C), a BCC structure dominates the PdCu NPs. Density functional theory (DFT) computations unravel a similar H binding strength and a much stronger OH binding of the PdCu BCC surface (cf. FCC surface), both of which are simultaneously close to those of Pt surfaces. The synergistic optimization of both H and OH binding strengths is responsible for the enhancement of HOR activity on BCC-phased PdCu, which could serve as an efficient anode catalyst for anion-exchange membrane fuel cells. This work might open a new route to develop efficient HOR catalysts from the perspective of crystalline structure transformation.

Alkali Metal Cation Effects in Structuring Pt, Rh, and Au Surfaces through Cathodic Corrosion.

Cathodic corrosion is an electrochemical etching process that alters metallic surfaces by creating nanoparticles and a variety of etching features. Because these features typically have a preferential orientation, cathodic corrosion can be applied to modify and nanostructure electrode surfaces. However, this application of cathodic corrosion is currently limited by an insufficient chemical understanding of its underlying mechanism. This includes the role of alkali metal cations, which are thought to be crucial in both enabling cathodic corrosion and controlling its final facet preference. This work addresses this knowledge gap by exploring the cathodic corrosion of Pt, Rh, and Au in LiOH, NaOH, and KOH through both experimental and theoretical methods. These methods demonstrate that cations are adsorbed during cathodic corrosion and play a major role in controlling the onset potential and final surface morphology in cathodic corrosion. Interestingly, an equally significant role appears to be played by adsorbed hydrogen, based on calculations using literature density functional theory data. Considering the significance of both hydrogen and electrolyte cations, it is hypothesized that cathodic corrosion might proceed via an intermediate ternary metal hydride. This fundamental insight leads to both metal-specific recommendations and more general guidelines for applying cathodic corrosion to structure metallic surfaces.

Effect of Step Density and Orientation on the Apparent pH Dependence of Hydrogen and Hydroxide Adsorption on Stepped Platinum Surfaces.

The effect of the alkali-metal cation (Li+, Na+, K+, and Cs+) on the non-Nernstian pH shift of the Pt(554) and Pt(533) step-associated voltammetric peak is elucidated over a wide pH window (1-13), through computation and experiment. In conjunction with our previously reported study on Pt(553), the non-Nernstian pH shift of the step-induced peak is found to be independent of the step density and the step orientation. In our prior work, we explained the sharp peak as due to the exchange between adsorbed hydrogen and hydroxyl along the step and the non-Nernstian shift as a result of the adsorption of an alkali-metal cation and its subsequent weakening of hydroxyl adsorption. Our density functional theory results support this same mechanism on Pt(533) and capture the effect of alkali-metal cation identity and alkali cation coverage well, where increasing electrolyte pH and cation concentration leads to increased cation coverage and a greater weakening effect on hydroxide adsorption. This work paints a consistent picture for the mechanism of these effects, expanding our fundamental understanding of the electrode/electrolyte interface and practical ability to control hydrogen and hydroxyl adsorption thermodynamics via the electrolyte composition, important for improving fuel cell and electrolyzer performance.

Co-adsorption of Cations as the Cause of the Apparent pH Dependence of Hydrogen Adsorption on a Stepped Platinum Single-Crystal Electrode.

The successful deployment of advanced energy-conversion systems depends critically on our understanding of the fundamental interactions of the key adsorbed intermediates (hydrogen *H and hydroxyl *OH) at electrified metal-aqueous electrolyte interfaces. The effect of alkali metal cations (Li+ , Na+ , K+ , Cs+ ) on the non-Nernstian pH shift of the step-related voltammetric peak of the Pt(553) electrode is investigated over a wide pH window (1 to 13) by means of experimental and computational methods. The co-adsorbed alkali cations along the step weaken the OH adsorption at the step sites, causing a positive shift of the potential of the step-related peak on Pt(553). Density functional calculations explain the observations on the identity and concentration of alkali cations on the non-Nernstian pH shift, and demonstrate that cation-hydroxyl co-adsorption causes the apparent pH dependence of "hydrogen" adsorption in the step sites of platinum electrodes.

First-Principles Calculation of Pt Surface Energies in an Electrochemical Environment: Thermodynamic Driving Forces for Surface Faceting and Nanoparticle Reconstruction.

Platinum is a widely used catalyst in aqueous and electrochemical environments. The size and shape of Pt nanoparticles and the faceting (and roughness) of extended Pt surfaces change during use in these environments due to dissolution, growth, and reconstruction. Further, many Pt nanoparticle synthesis techniques are carried out in an aqueous environment. The surface structures formed are impacted by the relative surface energies of the low index facets in these environments. Density functional theory is used to calculate the surface energy of the low index facets of platinum as a function of electrochemical potential and coverage of adsorbed hydrogen, hydroxide, oxygen, and the formation of surface oxide in an aqueous environment. Whereas Pt(111) is the lowest energy bare surface in vacuum, the strong adsorption of hydrogen to Pt(100) at low potentials and of hydroxide to Pt(110) and oxygen to Pt(100) at high potentials drives these surfaces to be more stable in an electrochemical environment. We experimentally conditioned a polycrystalline platinum electrode by cycling the potential and find a growth in the total area as well as in the fraction of 110 and 100 sites, which are lower in energy at potentials where dissolved Pt is deposited or surface oxide is reduced. Further, we find that the lower surface energy of Pt(100) at low potentials may play a role in the growth of tetrahexahedral nanoparticles seen on square wave cycling of spherical Pt nanoparticles. Wulff constructions are presented as a function of Pt electrode potential.