Impact of Pt(hkl) Electrode Surface Structure on the Electrical Double Layer Capacitance.

The classical theory of the electrical double layer (EDL) does not consider the effects of the electrode surface structure on the EDL properties. Moreover, the best agreement between the traditional EDL theory and experiments has been achieved so far only for a very limited number of ideal systems, such as liquid metal mercury electrodes, for which it is challenging to operate with specific surface structures. In the case of solid electrodes, the predictive power of classical theory is often not acceptable for electrochemical energy applications, e.g., in supercapacitors, due to the effects of surface structure, electrode composition, and complex electrolyte contributions. In this work, we combine ab initio molecular dynamics (AIMD) simulations and electrochemical experiments to elucidate the relationship between the structure of Pt(hkl) surfaces and the double-layer capacitance as a key property of the EDL. Flat, stepped, and kinked Pt single crystal facets in contact with acidic HClO4 media are selected as our model systems. We demonstrate that introducing specific defects, such as steps, can substantially reduce the EDL capacitances close to the potential of zero charge (PZC). Our AIMD simulations reveal that different Pt facets are characterized by different net orientations of the water dipole moment at the interface. That allows us to rationalize the experimentally measured (inverse) volcano-shaped capacitance as a function of the surface step density.

Periodicity in the Electrochemical Dissolution of Transition Metals.

Extensive research efforts are currently dedicated to the search for new electrocatalyst materials in which expensive and rare noble metals are replaced with cheaper and more abundant transition metals. Recently, numerous alloys, oxides, and composites with such metals have been identified as highly active electrocatalysts through the use of high-throughput screening methods with the help of activity descriptors. Up to this point, stability has lacked such descriptors. Hence, we elucidate the role of intrinsic metal/oxide properties on the corrosion behavior of representative 3d, 4d, and 5d transition metals. Electrochemical dissolution of nine transition metals is quantified using online inductively coupled plasma mass spectrometry (ICP-MS). Based on the obtained dissolution data in alkaline and acidic media, we establish clear periodic correlations between the amount of dissolved metal, the cohesive energy of the metal atoms (Ecoh ), and the energy of oxygen adsorption on the metal (ΔHO,ads ). Such correlations can support the knowledge-driven search for more stable electrocatalysts.

Kinetics of pH-dependent interactions between PD-1 and PD-L1 immune checkpoint proteins from molecular dynamics.

Immune checkpoint blockade of signaling pathways such as PD-1/PD-L1 has recently opened up a new avenue for highly efficient immunotherapeutic strategies to treat cancer. Since tumor microenvironments are characterized by lower pH (5.5-7.0), pH-dependent protein-ligand interactions can be exploited as efficient means to regulate drug affinity and specificity for a variety of malignancies. In this article, we investigate the mechanism and kinetics of pH-dependent binding and unbinding processes for the PD-1/PD-L1 checkpoint pair employing classical molecular dynamics simulations. Two representative pH levels corresponding to circumneutral physiological conditions of blood (pH 7.4) and acidic tumor microenvironment (pH 5.5) are considered. Our calculations demonstrate that pH plays a key role in protein-ligand interactions with small pH changes leading to several orders of magnitude increase in binding affinity. By identifying the binding pocket in the PD-1/PD-L1 complex, we show a pivotal role of the His68 protonation state of PD-1in the complex stabilization at low pH. The results on the reaction rate constants are in qualitative agreement with available experimental data. The obtained molecular details are important for further engineering of binding/unbinding kinetics to formulate more efficient immune checkpoint blockade strategies.

Ferroelectric Tunnel Junctions Enhanced by a Polar Oxide Barrier Layer.

Ferroelectric tunnel junctions (FTJs) have recently aroused significant interest due to the interesting physics controlling their properties and potential application in nonvolatile memory devices. In this work, we propose a new concept to design high-performance FTJs based on ferroelectric/polar-oxide composite barriers. Using density functional theory calculations, we model electronic and transport properties of LaNiO3/PbTiO3/LaAlO3/LaNiO3 tunnel junctions and demonstrate that an ultrathin polar LaAlO3(001) layer strongly enhances their performance. We predict a tunneling electroresistance (TER) effect in these FTJs with an OFF/ON resistance ratio exceeding a factor of 104 and ON state resistance as low as about 1 kΩµm2. Such an enhanced performance is driven by the ionic charge at the PbTiO3/LaAlO3 interface, which significantly increases transmission across the FTJ when the ferroelectric polarization of PbTiO3 is pointing against the intrinsic electric field produced by this ionic charge. This is due to the formation of a two-dimensional (2D) electron or hole gas, depending on the LaAlO3 termination being (LaO)+ or (AlO2)-, respectively, which is formed to screen the polarization charge of the nonuniform polarization state. This 2D electron (hole) gas can be switched ON and OFF by the reversal of ferroelectric polarization, resulting in the giant TER effect. The proposed design suggests a new direction for creating FTJs with a stable and reversible ferroelectric polarization, a sizable TER effect, and a low-resistance-area product, as required for memory applications.

Tunneling Hot Spots in Ferroelectric SrTiO3.

Strontium titanate (SrTiO3) is the "silicon" in the emerging field of oxide electronics. While bulk properties of this material have been studied for decades, new unexpected phenomena have recently been discovered at the nanoscale, when SrTiO3 forms an ultrathin film or an atomically sharp interface with other materials. One of the striking discoveries is room-temperature ferroelectricity in strain-free ultrathin films of SrTiO3 driven by the TiSr antisite defects, which generate a local dipole moment polarizing the surrounding nanoregion. Here, we demonstrate that these polar defects are not only responsible for ferroelectricity, but also propel the appearance of highly conductive channels, "hot spots", in the ultrathin SrTiO3 films. Using a combination of scanning probe microscopy experimental studies and theoretical modeling, we show that the hot spots emerge due to resonant tunneling through localized electronic states created by the polar defects and that the tunneling conductance of the hot spots is controlled by ferroelectric polarization. Our finding of the polarization-controlled defect-assisted tunneling reveals a new mechanism of resistive switching in oxide heterostructures and may have technological implications for ferroelectric tunnel junctions. It is also shown that the conductivity of the hot spots can be modulated by mechanical stress, opening a possibility for development of conceptually new electronic devices with mechanically tunable resistive states.

Defect-Assisted Tunneling Electroresistance in Ferroelectric Tunnel Junctions.

Recent experimental results have demonstrated ferroelectricity in thin films of SrTiO_{3} induced by antisite Ti_{Sr} defects. This opens a possibility to use SrTiO_{3} as a barrier layer in ferroelectric tunnel junctions (FTJs)-emerging electronic devices promising for applications in nanoelectronics. Here using density functional theory combined with quantum-transport calculations applied to a prototypical Pt/SrTiO_{3}/Pt FTJ, we demonstrate that the localized in-gap energy states produced by the antisite Ti_{Sr} defects are responsible for the enhanced electron tunneling conductance which can be controlled by ferroelectric polarization. Our tight-binding modeling, which takes into account multiple defects, shows that the predicted defect-assisted tunneling electroresistance effect is greatly amplified when the defect energy levels are brought to the Fermi energy by one of the polarization states. Our results have implications for FTJs based on conventional ferroelectric barriers with defects and can be employed for the design of new types of FTJs with enhanced performance.

First-principles study of adsorption-desorption kinetics of aqueous V2+/V3+ redox species on graphite in a vanadium redox flow battery.

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (112[combining macron]0) graphite facets with water and aqueous V2+/V3+ redox species at 300 K employing Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V2+/V3+ species. The formation of V-O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

Ab initio modeling of Fe(II) adsorption and interfacial electron transfer at goethite (α-FeOOH) surfaces.

Goethite (α-FeOOH) surfaces represent one of the most ubiquitous redox-active interfaces in the environment, playing an important role in biogeochemical metal cycling and contaminant residence in the subsurface. Fe(II)-catalyzed recrystallization of goethite is a fundamental process in this context, but the proposed Fe(II)aq-Fe(III)goethite electron and iron atom exchange mechanism of recrystallization remains poorly understood at the atomic level. We examine the adsorption of aqueous Fe(II) and subsequent interfacial electron transfer (ET) between adsorbed Fe(II) and structural Fe(III) at the (110) and (021) goethite surfaces using density functional theory calculations including Hubbard U corrections (DFT + U) aided by ab initio molecular dynamics simulations. We investigate various surface sites for the adsorption of Fe(2+)(H2O)6 in different coordination environments. Calculated energies for adsorbed complexes at both surfaces favor monodentate complexes with reduced 4- and 5-fold coordination over higher-dentate structures and 6-fold coordination. The hydrolysis of H2O ligands is observed for some pre-ET adsorbed Fe(II) configurations. ET from the adsorbed Fe(II) into the goethite lattice is calculated to be energetically uphill always, but simultaneous proton transfer from H2O ligands of the adsorbed complexes to the surface oxygen species stabilizes post-ET states. We find that surface defects such as oxygen vacancies near the adsorption site also can stabilize post-ET states, enabling the Fe(II)aq-Fe(III)goethite interfacial electron transfer reaction implied from experiments to proceed.

Multiscale model of metal alloy oxidation at grain boundaries.

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3-10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2-1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales.

Electron transport in pure and substituted iron oxyhydroxides by small-polaron migration.

Iron oxyhydroxides (FeOOH) are common crystalline forms of iron that play a critical role in technology and the natural environment via a variety of important reduction-oxidation reactions, including electrical semiconduction as an aspect. However, a basic understanding of the electron transport properties of these systems is still lacking. We examine the electron mobility in goethite (α-FeOOH), akaganéite (ß-FeOOH), and lepidocrocite (γ-FeOOH) polymorphs by means of density functional theory based (DFT+U) calculations. We show that room temperature charge transport should be dominated by the small-polaron hopping type, and that the attendant mobility should be highest for pure goethite and akaganéite. Hopping pathways through the various lattices are discussed in terms of individual electron exchange steps and rates for each. Given the usual occurrence of compositional impurities in natural iron oxyhydroxides, we also investigate the effect of common stoichiometric defects on the electron hopping activation energies such as Al and Cr substitutional cations in goethite, and Cl anions in the channels of akaganéite.

Influence of Alkali Metal Cations on the Oxygen Reduction Activity of Pt5Y and Pt5Gd Alloys.

Electrolyte species can significantly influence the electrocatalytic performance. In this work, we investigate the impact of alkali metal cations on the oxygen reduction reaction (ORR) on active Pt5Gd and Pt5Y polycrystalline electrodes. Due to the strain effects, Pt alloys exhibit a higher kinetic current density of ORR than pure Pt electrodes in acidic media. In alkaline solutions, the kinetic current density of ORR for Pt alloys decreases linearly with the decreasing hydration energy in the order of Li+ > Na+ > K+ > Rb+ > Cs+, whereas Pt shows the opposite trend. To gain further insights into these experimental results, we conduct complementary density functional theory calculations considering the effects of both electrode surface strain and electrolyte chemistry. The computational results reveal that the different trends in the ORR activity in alkaline media can be explained by the change in the adsorption energy of reaction intermediates with applied surface strain in the presence of alkali metal cations. Our findings provide important insights into the effects of the electrolyte and the strain conditions on the electrocatalytic performance and thus offer valuable guidelines for optimizing Pt-based electrocatalysts.

Coupling nitrate capture with ammonia production through bifunctional redox-electrodes.

Nitrate is a ubiquitous aqueous pollutant from agricultural and industrial activities. At the same time, conversion of nitrate to ammonia provides an attractive solution for the coupled environmental and energy challenge underlying the nitrogen cycle, by valorizing a pollutant to a carbon-free energy carrier and essential chemical feedstock. Mass transport limitations are a key obstacle to the efficient conversion of nitrate to ammonia from water streams, due to the dilute concentration of nitrate. Here, we develop bifunctional electrodes that couple a nitrate-selective redox-electrosorbent (polyaniline) with an electrocatalyst (cobalt oxide) for nitrate to ammonium conversion. We demonstrate the synergistic reactive separation of nitrate through solely electrochemical control. Electrochemically-reversible nitrate uptake greater than 70 mg/g can be achieved, with electronic structure calculations and spectroscopic measurements providing insight into the underlying role of hydrogen bonding for nitrate selectivity. Using agricultural tile drainage water containing dilute nitrate (0.27 mM), we demonstrate that the bifunctional electrode can achieve a 8-fold up-concentration of nitrate, a 24-fold enhancement of ammonium production rate (108.1 ug h-1 cm-2), and a >10-fold enhancement in energy efficiency when compared to direct electrocatalysis in the dilute stream. Our study provides a generalized strategy for a fully electrified reaction-separation pathway for modular nitrate remediation and ammonia production.

Revealing Elusive Intermediates of Platinum Cathodic Corrosion through DFT Simulations.

Cathodic corrosion of metals discovered more than 120 years ago remains a poorly understood electrochemical process. It is believed that the corrosion intermediates formed during cathodic polarization are extremely short-lived species because of their high reactivity. Together with the concurrent vigorous hydrogen evolution, this makes it challenging to investigate the reaction mechanism and detect the intermediates experimentally. From a computational standpoint, the process also presents a serious challenge as it occurs at rather low negative potentials in concentrated alkaline solutions. Here, we use density-functional-theory calculations to elucidate the identity of reaction intermediates and their reactivity at the Pt(111)/electrolyte interface. By controlling the electrode potential in an experimentally relevant region through constant Fermi-level molecular dynamics, we reveal the formation of alkali cation-stabilized Pt hydrides as intermediates of cathodic corrosion. The results also suggest that the found Pt anions could discharge at the interface to produce H2 by reacting with either surface-bound hydrogen species or solution water molecules.

Molecular-Level Control over Ionic Conduction and Ionic Current Direction by Designing Macrocycle-Based Ionomers.

Poor ionic conductivity of the catalyst-binding, sub-micrometer-thick ionomer layers in energy conversion and storage devices is a huge challenge. However, ionomers are rarely designed keeping in mind the specific issues associated with nanoconfinement. Here, we designed nature-inspired ionomers (calix-2) having hollow, macrocyclic, calix[4]arene-based repeat units with precise, sub-nanometer diameter. In ≤100 nm-thick films, the in-plane proton conductivity of calix-2 was up to 8 times higher than the current benchmark ionomer Nafion at 85% relative humidity (RH), while it was 1-2 orders of magnitude higher than Nafion at 20-25% RH. Confocal laser scanning microscopy and other synthetic techniques allowed us to demonstrate the role of macrocyclic cavities in boosting the proton conductivity. The systematic self-assembly of calix-2 chains into ellipsoids in thin films was evidenced from atomic force microscopy and grazing incidence small-angle X-ray scattering measurements. Moreover, the likelihood of alignment and stacking of macrocyclic units, the presence of one-dimensional water wires across this macrocycle stacks, and thus the formation of long-range proton conduction pathways were suggested by atomistic simulations. We not only did see an unprecedented improvement in thin-film proton conductivity but also saw an improvement in proton conductivity of bulk membranes when calix-2 was added to the Nafion matrices. Nafion-calix-2 composite membranes also took advantage of the asymmetric charge distribution across calix[4]arene repeat units collectively and exhibited voltage-gating behavior. The inclusion of molecular macrocyclic cavities into the ionomer chemical structure can thus emerge as a promising design concept for highly efficient ion-conducting and ion-permselective materials for sustainable energy applications.

Mechanistic Study of IrO2 Dissolution during the Electrocatalytic Oxygen Evolution Reaction.

Understanding the mechanistic interplay between the activity and stability of water splitting electrocatalysts is crucial for developing efficient and durable water electrolyzers. Ir-based materials are among the best catalysts for the oxygen evolution reaction (OER) in acidic media, but their degradation mechanisms are not completely understood. Here, through first-principles calculations we investigate iridium dissolution at the IrO2(110)/water interface. Simulations reveal that the surface-bound IrO2OH species formed upon iridium dissolution should be thermodynamically stable in a relatively wide potential window undergoing transformations into IrVI (as IrO3) at high anodic potentials and IrIII (as Ir(OH)3) at low anodic potentials. The identified high-valence surface-bound dissolution intermediates of Ir are determined to display greater OER activities than the pristine IrO2(110) surface in agreement with the experimentally observed high activity of an amorphous hydrated IrOx surface layer. Combined with recent experimental results, our simulations illuminate the mechanistic details of the degradation mechanism of IrO2 and how it couples to electrocatalytic OER.

Ab Initio Modeling of Transition Metal Dissolution from the LiNi0.5Mn1.5O4 Cathode.

Irreversible dissolution of transition metals (TMs) from cathode materials in lithium-ion batteries (LIBs) represents a serious challenge for the application of high-energy-density LIBs. Despite substantial improvements achieved by Ni doping of the LiMn2O4 spinel, the promising high-voltage LiNi0.5Mn1.5O4 (LNMO) cathode material still suffers from the loss of electro-active materials (Mn and Ni). This process contributes to the formation of solid-electrolyte interfaces and capacity loss severely limiting the battery life cycle. Here, we combine static and ab initio molecular dynamics free energy calculations based on the density functional theory to investigate the mechanism and kinetics of TM dissolution from LNMO into the liquid organic electrolyte. Our calculations help deconvolute the impact of various factors on TM dissolution rates such as the presence of surface protons and oxygen vacancies and the nature of TMs and electrolyte species. The present study also reveals a linear relationship between adsorption strength of the electrolyte species and TM dissolution barriers that should help design electrode/electrolyte interfaces less vulnerable to TM dissolution.

Mechanistic Theoretical Investigation of Self-Discharge Reactions in a Vanadium Redox Flow Battery.

Compared to the studies of new electrolyte and electrode chemistries aimed to push the energy and power density of battery systems, investigations of self-discharge reactions contributing to capacity fading are still very limited, especially at the molecular level. Herein, we present a computational study of oxidation-reduction reactions between vanadium ions in solution leading to battery self-discharge due to the crossover of vanadium species through the membrane in all-vanadium redox flow batteries (RFB). By utilizing Car-Parrinello molecular dynamics (CPMD) based metadynamics simulations in combination with the Marcus electron transfer theory, we examine the energetics of condensation reactions between aqueous vanadium ions to form dimers and their subsequent dissociation into vanadium species of different oxidation states after electron transfer has occurred. Our results suggest that multiple self-discharge reaction pathways could be possible under the vanadium RFB operation conditions. The study underscores the complexity of vanadium polymerization reactions in aqueous solutions with coupled electron and proton transfer processes that can lead to the formation of various mixed-valence vanadium polymeric structures.

Ab Initio Metadynamics Study of the VO2+/VO2+ Redox Reaction Mechanism at the Graphite Edge/Water Interface.

Redox flow batteries (RFBs) are promising electrochemical energy storage systems, for which development is impeded by a poor understanding of redox reactions occurring at electrode/electrolyte interfaces. Even for the conventional all-vanadium RFB chemistry employing V2+/V3+ and VO2+/VO2+ couples, there is still no consensus about the reaction mechanism, electrode active sites, and rate-determining step. Herein, we perform Car-Parrinello molecular dynamics-based metadynamics simulations to unravel the mechanism of the VO2+/VO2+ redox reaction in water at the oxygen-functionalized graphite (112̅0) edge surface serving as a representative carbon-based electrode. Our results suggest that during the battery discharge aqueous VO2+/VO2+ species adsorb at the surface C-O groups as inner-sphere complexes, exhibiting faster adsorption/desorption kinetics than V2+/V3+, at least at low vanadium concentrations considered in our study. We find that this is because (i) VO2+/VO2+ conversion does not involve the slow transfer of an oxygen atom, (ii) protonation of VO2+ is spontaneous and coupled to interfacial electron transfer in acidic conditions to enable VO2+ formation, and (iii) V3+ found to be strongly bound to oxygen groups of the graphite surface features unfavorable desorption kinetics. In contrast, the reverse process taking place upon charging is expected to be more sluggish for the VO2+/VO2+ redox couple because of both unfavorable deprotonation of the VO2+ water ligands and adsorption/desorption kinetics.

Ab Initio Modeling of Bulk and Intragranular Diffusion in Ni Alloys.

Knowledge of solid-state and interfacial species diffusion kinetics is of paramount importance for understanding mechanisms of grain boundary (GB) oxidation causing environmental degradation and cracking of Ni-base structural alloys. In this study, first-principles calculations of vacancy-mediated diffusion are performed across a wide series of alloying elements commonly used in Ni-based superalloys, as well as interstitial diffusion of atomic oxygen and sulfur in the bulk, at the (111) surface, ⟨110⟩ symmetric tilt GBs of Ni corresponding to model low- (Σ = 3/(111)) and high-energy (Σ = 9/(221)) GBs. A substantial enhancement of diffusion is found for all species at the high-energy GB as compared with the bulk and the low-energy GB, with Cr, Mn, and Ti exhibiting remarkably small activation barriers (<0.1 eV; ~10 times lower than in the bulk). Calculations also show that the bulk diffusion mechanism and kinetics differ for oxygen and sulfur, with oxygen having a faster mobility and preferentially diffusing through the tetrahedral interstitial sites in Ni matrix, where it can be trapped in a local minimum.