Cooperative Effects Drive Water Oxidation Catalysis in Cobalt Electrocatalysts through the Destabilization of Intermediates.

A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple overlapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (∼0.34 eV/monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O2 evolution onset coincide due to weaker binding and destabilization (∼0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

Electro-inductive Effect Dominates Vibrational Frequency Shifts of Conjugated Probes on Gold Electrodes.

Interfacial electric fields play a critical role in electrocatalysis and are often characterized by using vibrational probes attached to an electrode surface. Understanding the physical principles dictating the impact of the applied electrode potential on the vibrational probe frequency is important. Herein, a comparative study is performed for two molecular probes attached to a gold electrode. Both probes contain a nitrile (CN) group, but 4-mercaptobenzonitrile (4-MBN) exhibits continuous conjugation from the electrode through the nitrile group, whereas this conjugation is interrupted for 2-(4-mercaptophenyl)acetonitrile (4-MPCN). Periodic density functional theory calculations predict that the CN vibrational frequency shift of the 4-MBN system is dominated by induction, which is a through-bond polarization effect, leading to a strong potential dependence that does not depend significantly on the orientation of the CN bond relative to the surface. In contrast, the CN vibrational frequency shift of the 4-MPCN system is influenced less by induction and more by through-space electric field effects, leading to a weaker potential dependence and a greater orientation dependence. These theoretical predictions were confirmed by surface-enhanced Raman spectroscopy experiments. Balancing through-bond and through-space electrostatic effects may assist in the fundamental understanding and design of electrocatalytic systems.

Phenol as a Tethering Group to Gold Surfaces: Stark Response and Comparison to Benzenethiol.

Understanding the adsorption of organic molecules on metals is important in numerous areas of surface science, including electrocatalysis, electrosynthesis, and biosensing. While thiols are commonly used to tether organic molecules on metals, it is desirable to broaden the range of anchoring groups. In this study, we use a combined spectroelectrochemical and computational approach to demonstrate the adsorption of 4-cyanophenols (CPs) on polycrystalline gold. Using the nitrile stretching vibration as a marker, we confirm the adsorption of CP on the gold electrode and compare our results with those obtained for the thiol counterpart, 4-mercaptobenzonitirle (MBN). Our results reveal that CP adsorbs on the gold electrode via the OH linker, as evidenced by the similarity in the direction and magnitude of the nitrite Stark shifts for CP and MBN. This finding paves the way for exploring new approaches to modify electrode surfaces for controlled reactivity. Furthermore, it highlights adsorption on metals as an important step in the electroreactivity of phenols.

Inferring the Energetics of CO2-Aniline Adduct Formation from Vibrational Spectroscopy.

Control of atmospheric CO2 is an important contemporary scientific and engineering challenge. Toward this goal, the reaction of CO2 with amines to form carbamate bonds is an established method for CO2 capture. However, controllable reversal of this reaction remains difficult and requires tuning the energetics of the carbamate bond. Through IR spectroscopy, we show that a characteristic frequency observed upon carbamate formation varies as a function of the substituent's Hammett parameter for a family of para-substituted anilines. We present computational evidence that the vibrational frequency of the adducted CO2 serves as a predictor of the energy of formation of the carbamate. Electron donating groups typically enhance the driving force of carbamate formation by transferring more charge to the adducted CO2 and thus increasing the occupancy of the antibonding orbital in the carbon-oxygen bonds. Increased occupancy of the antibonding orbital within adducted CO2 indicates a weaker bond, leading to a red-shift in the characteristic carbamate frequency. Our work serves the large field of CO2 capture research where spectroscopic observables, such as IR frequencies, are more easily obtainable and can stand in as a descriptor of driving forces.

Inductive Effect Alone Cannot Explain Lewis Adduct Formation and Dissociation at Electrode Interfaces.

Understanding breaking and formation of Lewis bonds at an electrified interface is relevant to a large range of phenomena, including electrocatalysis and electroadsorption. The complexities of interfacial environments and associated reactions often impede a systematic understanding of this type of bond at interfaces. To address this challenge, we report the creation of a main group classic Lewis acid-base adduct on an electrode surface and its behavior under varying electrode potentials. The Lewis base is a self-assembled monolayer of mercaptopyridine and the Lewis acid is BF3, forming a Lewis bond between nitrogen and boron. The bond is stable at positive potentials but cleaves at potentials more negative of approximately -0.3 V vs Ag/AgCl without an associated current. We also show that if the Lewis acid BF3 is supplied from a reservoir of Li+BF4- electrolyte, the cleavage is completely reversible. We propose that the N-B Lewis bond is affected both by the field-induced intramolecular polarization (electroinduction) and by the ionic structures and ionic equilibria near the electrode. Our results indicate that the second effect is responsible for the Lewis bond cleavage at negative potentials. This work is relevant to understanding the fundamentals of electrocatalytic and electroadsorption processes.

Distinguishing between the Electrostatic Effects and Explicit Ion Interactions in a Stark Probe.

Vibrational Stark probes are incisive tools for measuring local electric fields in a wide range of chemical environments. The interpretation of the frequency shift often gets complicated due to the specific interactions of the probe, such as hydrogen bonding and Lewis bonding. Therefore, it is important to distinguish between the pure electrostatic response and the response due to such specific interactions. Here we report a molecular system that is sensitive to both the Stark effect from a single ion and the explicit Lewis bonding of ions with the probe. The molecule consists of a crown ether with an appended benzonitrile. The crown captures cations of various charges, and the electric field from the ions is sensed by the benzonitrile probe. Additionally, the lone pair of the benzonitrile can engage in Lewis interactions with some of the ions by donating partial charge density to the ions. Our system exhibits both of these effects and therefore is a suitable test bed for distinguishing between the pure electrostatic and the Lewis interactions. Our computational results show that the electrostatic influence of the ion is operative at large distances, while the Lewis interaction becomes important only within distances that permit orbital overlap. Our results may be useful for using the nitrile probe for measuring electrostatic and coordination effects in complex ionic environments such as the electrode-electrolyte interfaces.

Polarizable Anionic Sublattices Can Screen Molecular Dipoles in Noncentrosymmetric Inorganic-Organic Hybrids.

We report the growth and photophysical characterization of two polar hybrid lead halide phases, methylenedianiline lead iodide and bromide, (MDA)Pb2I6 and (MDA)Pb2Br6, respectively. The phases crystallize in noncentrosymmetric space group Fdd2, which produces a highly oriented molecular dipole moment that gives rise to second harmonic generation (SHG) upon excitation at 1064 nm. While both compositions are isostructural, the size dependence of the SHG signal suggests that the bromide exhibits a stronger phase-matching response whereas the iodide exhibits a significantly weaker non-phase-matching signal. Similarly, fluorescence from (MDA)Pb2Br6 is observed around 630 nm below 75 K whereas only very weak luminescence from (MDA)Pb2I6 can be seen. We attribute the contrasting optical properties to differences in the character of the halide sublattice and postulate that the increased polarizability of the iodide ions acts to screen the local dipole moment, effectively reducing the local electric field in the crystals.

Direct Determination of Plasmon Enhancement Factor and Penetration Depths in Surface Enhanced IR Absorption Spectroscopy.

Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS) is a powerful tool for studying a wide range of surface and electrochemical phenomena. For most electrochemical experiments the evanescent field of an IR beam partially penetrates through a thin metal electrode deposited on top of an attenuated total reflection (ATR) crystal to interact with molecules of interest. Despite its success, a major problem that complicates quantitative interpretation of the spectra from this method is the ambiguity of the enhancement factor due to plasmon effects in metals. We developed a systematic method for measuring this, which relies upon independent determination of surface coverage by Coulometry of a surface-bound redox-active species. Following that, we measure the SEIRAS spectrum of the surface bound species, and from the knowledge of surface coverage, retrieve the effective molar absorptivity, εSEIRAS. Comparing this to the independently determined bulk molar absorptivity leads us to the enhancement factor f = εSEIRAS/εbulk. We report enhancement factors in excess of 1000 for the C-H stretches of surface bound ferrocene molecules. We additionally developed a methodical approach to measure the penetration depth of the evanescent field from the metal electrode into a thin film. Such systematic measure of the enhancement factor and penetration depth will help SEIRAS advance from a qualitative to a more quantitative method.

Controlling Water Delivery to an Electrochemical Interface with Surfactants.

Most electrochemical reactions require delivery of protons, often from water, to surface-adsorbed species. However, water also acts as a competitor to many such processes by directly reacting with the electrode, which necessitates using water in small amounts. Controlling the water content and structure near the surface is an important frontier in directing the reactivity and selectivity of electrochemical reactions. Surfactants accumulate near surfaces, and therefore, they can be used as agents to control interfacial water. Using mid-IR spectro-electrochemistry, we show that a modest concentration (1 mM) of the cationic surfactant CTAB in mixtures of 10 M water in an organic solvent (dDMSO) has a large effect on the interfacial water concentration, changing it by up to ∼35% in the presence of an applied potential. The major cause of water content change is displacement due to the accumulation or depletion of surfactants driven by potential. Two forces drive the surfactants to the electrode: the applied potential and the hydrophobic interactions with the water in the bulk. We have quantified their competition by varying the water content in the bulk. To our knowledge, for the first time, we have identified the electrochemical equivalent of the hydrophobic drive. For our system, a change in applied potential of 1 V has the same effect as adding a 0.55 mole fraction of water to the bulk. This work illustrates the significance of surfactants in the partitioning of water between the bulk and the surface and paves the way toward engineering interfacial water structures for controlling electrochemical reactions.

Modeling and Characterization of Exciplexes in Photoredox CO2 Reduction: Insights from Quantum Chemistry and Fluorescence Spectroscopy.

Interactions between excited-state arenes and amines can lead to the formation of structures with a distinct emission behavior. These excited-state complexes or exciplexes can reduce the ability of the arene to participate in other reactions, such as CO2 reduction, or increase the likelihood of degradation via Birch reduction. Exciplex geometries are necessary to understand photophysical behavior and probe degradation pathways but are challenging to calculate. We establish a detailed computational protocol for calculation, verification, and characterization of exciplexes. Using fluorescence spectroscopy, we first demonstrate the formation of exciplexes between excited-state oligo-(p-phenylene) (OPP), shown to successfully carry out CO2 reduction, and triethylamine. Time-dependent density functional theory is employed to optimize the geometries of these exciplexes, which are validated by comparing both emission energies and their solvatochromism with the experiment. Excited-state energy decomposition analysis confirms the predominant role played by charge transfer interactions in the red shift of emissions relative to the isolated excited-state OPP*. We find that although the exciplex emission frequency depends strongly on solvent dielectric, the extent of charge separation in an exciplex does not. Our results also suggest that the formation of solvent-separated ionic radical states upon complete electron transfer competes with exciplex formation in higher-dielectric solvents, thereby leading to reduced exciplex emission intensities in fluorescence experiments.

Can Brønsted Photobases Act as Lewis Photobases?

Dative bonding or Lewis acid-base chemistry underpins a large number of chemical phenomena in a variety of fields, such as catalysis, metal-ligand interactions, and surface chemistry. Developing light-controlled Lewis acid-base interactions could offer a new way of controlling and understanding such phenomena. Photoinduced proton transfer, that is, excited-state Brønsted acidity and basicity, has been extensively studied and applied. Here, in direct analogy to excited-state Brønsted basicity, we show that exciting a photobasic molecule with light generates a thermodynamic drive for the transfer of a Lewis acid from a donor to a photobasic molecule. We have used the archetypal BF3 as our Lewis acid and our photoactive Lewis bases are a family of quinolines, which are known Brønsted photobases as well. We have constructed the experimental Förster cycle for this system and have verified it computationally to demonstrate that a significant drive (0.2-0.7 eV) exists for the transfer of BF3 to a photoexcited quinoline. The magnitude of this drive is similar to those reported for Brønsted photobasicity in quinolines. Computational results from TDDFT and energy decomposition analysis show that the origin of such an effect is similar to the Brønsted photoactivity of these molecules, in that they follow the Hammett parameter of substituent groups. These results suggest that photobases may be capable of controlling the chemical phenomena beyond proton transfer and may open opportunities for a new handle in photocatalysis.

In Situ Investigation of Ultrafast Dynamics of Hot Electron-Driven Photocatalysis in Plasmon-Resonant Grating Structures.

Understanding the relaxation and injection dynamics of hot electrons is crucial to utilizing them in photocatalytic applications. While most studies have focused on hot carrier dynamics at metal/semiconductor interfaces, we study the in situ dynamics of direct hot electron injection from metal to adsorbates. Here, we report a hot electron-driven hydrogen evolution reaction (HER) by exciting the localized surface plasmon resonance (LSPR) in Au grating photoelectrodes. In situ ultrafast transient absorption (TA) measurements show a depletion peak resulting from hot electrons. When the sample is immersed in solution under -1 V applied potential, the extracted electron-phonon interaction time decreases from 0.94 to 0.67 ps because of additional energy dissipation channels. The LSPR TA signal is redshifted with delay time because of charge transfer and subsequent change in the dielectric constant of nearby solution. Plateau-like photocurrent peaks appear when exciting a 266 nm linewidth grating with p-polarized (on resonance) light, accompanied by a similar profile in the measured absorptance. Double peaks in the photocurrent measurement are observed when irradiating a 300 nm linewidth grating. The enhancement factor (i.e., reaction rate) is 15.6× between p-polarized and s-polarized light for the 300 nm linewidth grating and 4.4× for the 266 nm linewidth grating. Finite-difference time domain (FDTD) simulations show two resonant modes for both grating structures, corresponding to dipolar LSPR modes at the metal/fused silica and metal/water interfaces. To our knowledge, this is the first work in which LSPR-induced hot electron-driven photochemistry and in situ photoexcited carrier dynamics are studied on the same plasmon resonance structure with and without adsorbates.

Electric Fields Influence Intramolecular Vibrational Energy Relaxation and Line Widths.

Intramolecular vibrational energy relaxation (IVR) is fundamentally important to chemical dynamics. We show that externally applied electric fields affect IVR and vibrational line widths by changing the anharmonic couplings and frequency detunings between modes. We demonstrate this effect in benzonitrile for which prior experimental results show a decrease in vibrational line width as a function of applied electric field. We identify three major channels for IVR that depend on electric field. In the dominant channel, the electric field affects the frequency detuning, while in the other two channels, variation of anharmonic couplings as a function of field is the underlying mechanism. Consistent with experimental results, we show that the combination of all channels gives rise to reduced line widths with increasing electric field in benzonitrile. Our results are relevant for controlling IVR with external or internal fields and for gaining a more complete interpretation of line widths of vibrational Stark probes.

Adiabatic Frequency Conversion Using a Time-Varying Epsilon-Near-Zero Metasurface.

A time-dependent change in the refractive index of a material leads to a change in the frequency of an optical beam passing through that medium. Here, we experimentally demonstrate that this effect-known as adiabatic frequency conversion (AFC)-can be significantly enhanced by a nonlinear epsilon-near-zero-based (ENZ-based) plasmonic metasurface. Specifically, by using a 63-nm-thick metasurface, we demonstrate a large, tunable, and broadband frequency shift of up to ∼11.2 THz with a pump intensity of 4 GW/cm2. Our results represent a decrease of ∼10 times in device thickness and 120 times in pump peak intensity compared with the cases of bare, thicker ENZ materials for the similar amount of frequency shift. Our findings might potentially provide insights for designing efficient time-varying metasurfaces for the manipulation of ultrafast pulses.

Mechanistic Insights about Electrochemical Proton-Coupled Electron Transfer Derived from a Vibrational Probe.

Proton-coupled electron transfer (PCET) is a fundamental step in a wide range of electrochemical processes, including those of interest in energy conversion and storage. Despite its importance, several mechanistic details of such reactions remain unclear. Here, we have combined a proton donor (tertiary ammonium) with a vibrational Stark-shift probe (benzonitrile), to track the process from the entry of the reactants into the electrical double layer (EDL), to the PCET reaction associated with proton donation to the electrode, and the formation of products. We have used operando vibrational spectroscopy and periodic density functional theory under electrochemical bias to assign the reactant and product peaks and their Stark shifts. We have identified three main stages for the progress of the PCET reaction as a function of applied potential. First, we have determined the potential necessary for desolvation of the reactants and their entry into the polarizing environment of the EDL. Second, we have observed the appearance of product peaks prior to the onset of steady state electrochemical current, indicating formation of a stationary population of products that does not turn over. Finally, more negative of the onset potential, the electrode attracts additional reactants, displacing the stationary products and enabling steady state current. This work shows that the integration of a vibrational Stark-shift probe with a proton donor provides critical insight into the interplay between interfacial electrostatics and heterogeneous chemical reactions. Such insights cannot be obtained from electrochemical measurements alone.

Interfacial Polarization and Ionic Structure at the Ionic Liquid-Metal Interface Studied by Vibrational Spectroscopy and Molecular Dynamics Simulations.

Ionic liquids (ILs) have both fundamental and practical value in interfacial science and electrochemistry. However, understanding their behavior near a surface is challenging because of strong Coulomb interactions and large and irregular ionic sizes, which affect both their structure and energetics. To understand this problem, we present a combined experimental and computational study using a vibrational probe molecule, 4-mercaptobenzonitrile, inserted at the junction between a metal and a variety of ILs. The vibrational frequency of the nitrile in the probe molecule reports on the local solvation environment and the electrostatic field at this junction. Within the ethylmethyl imidazolium (EMIM+) cation family of ILs, we varied the anions over a range of sizes and types. Complementing our surface spectroscopy, we also ran molecular dynamics simulations of these interfaces to better understand the ionic structures that produced the measured fields. The magnitude of the frequency shifts, and thereby fields, shows a general correlation with the size of anions, with larger anions corresponding to smaller fields. We find that the source of this correlation is partial intercalation of smaller anions into the probe monolayer, resulting in tighter packing of ionic layers near the surface. Larger anions reduce the overall lateral ion packing density near the surface, which reduces the net charge per unit area and explains the smaller observed fields. The insight from this work is important for developing a fundamental picture of concentrated electrolytes near interfaces and can help with designing ILs to create tailored electric fields near an electrode.

Strong Propensity of Ionic Liquids in Their Aqueous Solutions for an Organic-Modified Metal Surface.

Understanding ionic structure and electrostatic environments near a surface has both fundamental and practical value. In electrochemistry, especially when room temperature ionic liquids (ILs) are involved, the complex ionic structure near the interface is expected to crucially influence reactions. Here we report evidence that even in dilute aqueous solutions of several ILs, the ions aggregate near the surface in ways that are qualitatively different from simple electrolytes. We have used a vibrational probe molecule, 4-mercaptobenzonitrile (MBN), tethered to a metal surface to monitor the behavior of the ionic layers. The characteristic nitrile vibrational frequency of this molecule has distinct values in the presence of pure water (∼2232 cm-1) and pure IL (for example, ∼2226 cm-1 for ethylmethylimidazolium tetrafluoroborate, [EMIM][BF4]). This difference reflects the local electrostatic field and the hydrogen-bonding variations between these two limiting cases. We tracked this frequency shift as a function of IL concentration in water all the way from pure water to pure IL. We report two important findings. First, only one nitrile peak is observed for the entire concentration range, indicating that at least on the length scale of the probe molecule water and ILs do not phase separate within the interface, and no heterogeneously distinct electrostatic environments are formed. Second, and more importantly, we find that even up to a significant mole fraction of bulk water (x ∼ 0.95), the nitrile frequency does not change from that indicative of a pure IL for [EMIM][BF4], indicating preferential aggregation of the ions near the surface. Because this behavior is very similar to surfactants, we chose an imidazolium cation with a longer side chain which resulted in behavior expected from a surfactant, with a preferential layer of the ions on the surface even in dilute water solutions (x ∼ 0.995). This observation indicates that even those ILs that are not nominally categorized as surfactants have a strong tendency to aggregate at the surface. Because ILs serve as electrolytes in a range of electrochemical reactions, including those requiring water, our results are likely useful for mechanistic understanding and tuning of such reactions.

Electric Fields at Metal-Surfactant Interfaces: A Combined Vibrational Spectroscopy and Capacitance Study.

Surfactants modulate interfacial processes. In electrochemical CO2 reduction, cationic surfactants promote carbon product formation and suppress hydrogen evolution. The interfacial field produced by the surfactants affects the energetics of electrochemical intermediates, mandating their detailed understanding. We have used two complementary tools-vibrational Stark shift spectroscopy which probes interfacial fields at molecular length scales and electrochemical impedance spectroscopy (EIS) which probes the entire double layer-to study the electric fields at metal-surfactant interfaces. Using a nitrile as a probe, we found that at open-circuit potentials, cationic surfactants produce larger effective interfacial fields (∼-1.25 V/nm) when compared to anionic surfactants (∼0.4 V/nm). At a high bulk surfactant concentration, the surface field reaches a terminal value, suggesting the formation of a full layer, which is also supported by EIS. We propose an electrostatic model that explains these observations. Our results help in designing tailored surfactants for influencing electrochemical reactions via the interfacial field effect.