Potential Step Experiments Research Articles

Assessing the dynamics of O2 desorption from cobalt phthalocyanine by in situ electrochemical scanning tunneling microscopy

We report here the in situ electrochemical scanning tunneling microscopy (ECSTM) study of cobalt phthalocyanine (CoPc)-catalyzed O2 evolution reaction (OER) and the dynamics of CoPc-O2 dissociation. The self-assembled CoPc monolayer is fabricated on Au(111) substrate and resolved by ECSTM in 0.1 M KOH electrolyte. The OH− adsorption on CoPc prior to OER is observed in ECSTM images. During OER, the generated O2 adsorbed on CoPc is observed in the CoPc monolayer. Potential step experiment is employed to monitor the desorption of OER-generated O2 from CoPc, which results in the decreasing surface coverage of CoPc-O2 with time. The rate constant of O2 desorption is evaluated through data fitting. The insights into the dynamics of Co-O2 dissociation at the molecular level via in situ imaging help understand the role of Co-O2 in oxygen reduction reaction (ORR) and OER.

Underpotential deposition of Cu onto Au(111) in the presence of acetate

The underpotential deposition (UPD) of Cu on Au(111) in the presence of acetate is investigated by cyclic voltammetry, potential step experiments, and in-situ STM imaging. The specific adsorption of acetate stabilizes the UPD monolayer (ML) of Cu on Au(111). Three distinct deposition processes are identified by cyclic voltammetry. The first two deposition processes corresponding to Cu sub-monolayer coverages are reversible. Strong kinetic effects arise for higher Cu coverage during the deposition and dissolution, which gradually lower the reversibility of the electrocrystallization process. Dissolution of the full Cu monolayer is shifted positively by about 0.3 V. In addition, bulk deposition is kinetically hindered for an extended potential region. The acetate coverage on the complete Cu monolayer is estimated to be 0.2–0.3 ML. It is proposed that adsorbed acetate on the Cu UPD ML is related to the kinetic hindrance observed in the experiments. (Surface) alloying of Cu and Au is observed by cyclic voltammetry and in-situ STM.

Unraveling the Dynamic Processes of Methanol Electrooxidation at Isolated Rhodium Sites by In Situ Electrochemical Scanning Tunneling Microscopy.

Materials with isolated single-atom Rh-N4 sites are emerging as promising and compelling catalysts for methanol electrooxidation. Herein, we carried out an in situ electrochemical scanning tunneling microscopy (ECSTM) investigation of the dynamic processes of methanol absorption and catalytic conversion in the rhodium octaethylporphyrin (RhOEP)-catalyzed methanol oxidation reaction at the molecular scale. The high-contrast RhOEP-CH3OH complex formed by methanol adsorption was visualized distinctly in the STM images. The Rh-C adsorption configuration of methanol on isolated rhodium sites was identified on the basis of a series of control experiments and theoretical simulation. The adsorption energy of methanol on RhOEP was obtained from quantitative analysis. In situ ECSTM experiments present an explicit description of the transformation of the intermediate species in the catalytic process. By qualitatively evaluating the rate constants of different stages in the reaction at the microscopic level, we considered the CO transformation/desorption as the critical step for determining the reaction dynamics. Methanol adsorption was found to be correlated with RhOEP oxidation in the initial stage of the reaction, and the dynamic information was revealed unambiguously by in situ potential step experiments. This work provides microscopic results for the catalytic mechanism of Rh-N4 sites for methanol electrooxidation, which is instructive for the rational design of the high-performance catalyst.

Single-Molecule Study on the Catalytic Role of Co–O2 Binding in ORR by In Situ ECSTM

We report here the in situ electrochemical scanning tunneling microscopy (ECSTM) study of O2 adsorption and reduction on cobalt porphyrin (CoOEP) and phthalocyanine (CoPc). Electrochemical measurements reveal higher ORR activity of CoOEP than CoPc. Self-assembled CoOEP and CoPc monolayers are fabricated on Au(111) substrates and molecularly resolved by ECSTM. The direct molecular imaging demonstrates that O2 adsorbs on CoII sites and barely on CoIII sites. The CoOEP–O2 and CoPc–O2 complexes exhibit high contrast in ECSTM images due to O2 binding. The surface coverage of CoOEP–O2 is ca. 1.4 times higher than that of CoPc–O2. The dynamics of O2 adsorption is measured quantitatively by fitting data from potential step experiments to obtain rate constants for O2 adsorption (kad) and dissociation (kdi) on Co centers. kad and kdi are higher on CoOEP than on CoPc, indicating higher dynamics of O2 binding and lower barriers to Co–O dissociation on CoOEP.

Probing the Synergistic Effects of Mg2+ on CO2 Reduction Reaction on CoPc by In Situ Electrochemical Scanning Tunneling Microscopy.

We report herein the in situ electrochemical scanning tunneling microscopy (ECSTM) study on the synergistic effect of Mg2+ in CO2 reduction reaction (CO2RR) catalyzed by cobalt phthalocyanine (CoPc). ECSTM measurement molecularly resolves the self-assembled CoPc monolayer on the Au(111) substrate. In the CO2 environment, high-contrast species are observed in the adlayer and assigned to the CO2 adsorption on CoPc. Furthermore, the contrast of the CO2-bound complex is higher in Mg2+-containing electrolytes than in Mg2+-free electrolytes, indicating the formation of the CoPc-CO2-Mg2+ complex. The surface coverage of adsorbed CO2 is positively correlated with the Mg2+ concentration as the additive in electrolytes up to a plateau of 30.8 ± 2.7% when c(Mg2+) > 30 mM. The potential step experiment indicates the higher CO2 adsorption dynamics in Mg2+-containing electrolytes than without Mg2+. The rate constants of CO2 adsorption and dissociation in different electrolytes are extracted from the data fitting of statistical results from in situ ECSTM experiments.

PH-Induced Changes in the SERS Spectrum of Thiophenol at Gold Electrodes during Cyclic Voltammetry.

Thiophenol is a model compound used in the study of self-assembly of arylthiols on gold surfaces. In particular, changes in the surface-enhanced Raman scattering (SERS) spectra of these self-assembled monolayers (SAMs) with a change of conditions have been ascribed to, for example, differences in orientation with respect to the surface, protonation state, and electrode potential. Here, we show that potential-induced changes in the SERS spectra of SAMs of thiophenol on electrochemically roughened gold surfaces can be due to local pH changes at the electrode. The changes observed during the potential step and cyclic voltammetry experiments are identical to those induced by acid–base switching experiments in a protic solvent. The data indicate that the potential-dependent spectral changes, assigned earlier to changes in molecular orientation with respect to the surface, can be ascribed to changes in the pH locally at the electrode. The pH at the electrode can change as much as several pH units during electrochemical measurements that reach positive potentials where oxidation of adventitious water can occur. Furthermore, once perturbed by applying positive potentials, the pH at the electrode takes considerable time to recover to that of the bulk solution. It is noted that the changes in pH even during cyclic voltammetry in organic solvents can be equivalent to the addition of strong acids, such as CF3SO3H, and such effects should be considered in the study of the redox chemistry of pH-sensitive redox systems and potential-dependent SERS in particular.

Electrochemical oxidation of Pt(111) beyond the place-exchange model

Oxide formation plays an important role in the degradation of Pt electrocatalysts. However, the exact oxide structure and reaction mechanism are not fully understood. Here, we used in situ surface X-ray diffraction experiments to resolve the oxide formation at a Pt(111) model electrode at potentials near the onset of the oxygen evolution reaction. Fast experiments are possible by using X-ray photons with a high kinetic energy in combination with a large 2D detector. By employing very low potential sweep rates we obtain a more ordered oxidized surface compared to literature data from potential step experiments. This demonstrates that the oxidation process is strongly governed by the reaction kinetics. The increased surface order enables us to disentangle two subsequent oxidation process; initially the place-exchange process, followed by the formation of a partially disordered oxide in which still 50% of the surface atoms reside on sites commensurate to the Pt(111) surface. The reduction experiments indicate that the place-exchange process is structurally reversible, whereas the disordered oxide causes the surface roughening observed during potential cycling. Despite the increased surface order, oxide superstructures are not observed. These results provide important insights in the oxidation and degradation process of Pt(111), which are valuable for the design of improved electrocatalysts and they rationalize operating procedures.

Insertion of Magnesium into Antimony Layers on Gold Electrodes:Kinetic Behaviour

AbstractMagnesium based secondary batteries are regarded as a viable alternative to the immensely popular Li‐ion systems. One of the largest challenges is the selection of a Mg anode material since the insertion/extraction processes are kinetically slow because of the large ionic radius and high charge density of Mg2+. In an attempt to bridge the gap between insertion measurements in 3D composite electrode materials and that in an idealized pure model system, we studied the insertion and diffusion of Mg in a thin, massive layer of Sb deposited on Au by using PITT, CV, and potential step experiments. Sb has been suggested as an insertion material because magnesium can form intermetallic compound with it. The layered crystal structure of Sb leads should facilitate formation of such an intermetallic phase. Mg insertion from a MACC/tetraglyme electrolyte into Sb starts 300 mV positive of the onset potential of Mg deposition as shown by cyclic voltammetry. The molar ratio of Mg to Sb agrees well with the stoichiometry of Mg3Sb2 alloy (Zintl‐phase). The diffusion coefficient of Mg‐insertion into Sb – layers and the charge transfer rate have been estimated by the above techniques. Such diffusion coefficients, albeit still somewhat “apparent”, are much more closely related to the true diffusion coefficient in the metal or alloy. The solid‐state diffusion coefficient of Mg into the Sb layers is in the range of 4–8×10−14 cm2 s−1. A very high Tafel slope of 370 mV/dec was found in potential step experiments. Mg insertion was further investigated by XPS measurements. Besides Mg and Sb, Al and Cl signals were also detected, particularly at the outer parts of the layer.

Analytical solutions for the diffusive mass transfer at cylindrical and hollow-cylindrical electrodes with reflective and transmissive boundary conditions

• Unified theory for the diffusive mass transfer at cylindrical electrodes. • Analytical solutions are infinite series involving Bessel functions. • Semi-Infinite diffusion results in improper integral representations. • Analytical solutions confirm numerical results obtained from Talbot’s NILT method. The theoretical treatment of cyclic voltammetry or chronoamperometry at cylindrical electrodes by means of convolutive modeling requires an a priori knowledge of the time-dependent mass transfer functions and of the diffusive flux of the electrochemically active species. In this paper, analytical solutions for both of these quantities are derived for cylindrical and hollow-cylindrical electrodes with reflective and transmissive boundaries by means of Laplace transformation techniques. Furthermore, explicit equations for the concentration profiles of a Cottrellian potential step experiment are provided. All of these expressions are given in terms of infinite series involving Bessel functions of the first and of the second kind. It is demonstrated that the summation of only a few terms of these infinite series is usually sufficient to accurately compute the desired time-dependent mass-transfer function or the current. This renders the numerical inversion of Laplace transformations, utilized so far, obsolete and represents a mathematical supplement to the recent theory.

In Situ Spectroelectrochemical Characterization Reveals Cytochrome-Mediated Electric Syntrophy in Geobacter Coculture.

Direct interspecies electron transfer (DIET) between microbial species prevails in some key microbial consortia. However, the electron transfer mechanism(s) in these consortia is controversial due to lack of efficient characterization methods. Here, we provide an in situ anaerobic spectroelectrochemical coculture cell (in situ ASCC) to induce the formation of DIET coculture biofilm on the interdigitated microelectrode arrays and characterize the electron transfer directly. Two typical Geobacter DIET cocultures, Geobacter metallireducens and wild-type Geobacter sulfurreducens (G.m&G.s) and G. metallireducens and a G. sulfurreducens strain deficient in citrate synthase (G.m&G.s-ΔgltA), were selected. In situ Raman and electrochemical Fourier transform infrared (FTIR) spectroscopy indicated that cytochromes are abundant in the electric syntrophic coculture. Cyclic voltammetry and potential step experiment revealed a diffusion-controlled electron transfer process and the electrochemical gating measurements further demonstrated a cytochrome-mediated electron transfer in the DIET coculture. Furthermore, the G.m&G.s-ΔgltA coculture displayed a higher redox conductivity than the G.m&G.s coculture, consistent with the existence of an intimate and efficient electrical connection between these two species. Our findings provide the first report of a redox-gradient-driven electron transport facilitated by c-type cytochromes in DIET coculture, supporting the model that DIET is mediated by cytochromes and suggest a platform to explore the other DIET consortia.

Adsorption and Oxidation Dynamics of Disperse Orange 3 on a Polycrystalline Pt Electrode Studied by In Situ Second Harmonic Generation

Adsorption mechanisms and electrochemical reaction mechanisms at the molecular level are fundamental issues in electrochemistry. Here, we used in situ second harmonic generation (SHG) combined with in situ UV–vis spectra and potential step techniques to investigate the dynamics of the adsorption and oxidation of 4-amino-4′-nitroazobenzene (disperse orange 3, DO3) molecules on a polycrystalline Pt electrode. Time-dependent SHG spectra with different polarization combinations under certain potential steps confirmed that the SHG intensity change in the DO3 molecules resulted from the number density change rather than the orientation angle change. A double potential step experiment and UV–vis spectra verified that the number density change arose from the cooperative effects of adsorption and oxidation of DO3 at the interfaces. Under an applied potential, the adsorption rate of DO3 was greater than the electrooxidation rate in the first hundred seconds until full coverage was achieved and the maximum SHG intensity was reached. Subsequently, the oxidation of DO3 dominated until equilibrium was established, while the SHG intensity stabilized. In addition, the time-dependent SHG spectra showed that the rate constants of the adsorption process and the oxidation reaction were strongly dependent on the potential. This work provides in-depth insights into the adsorption and electrochemical reaction at electrode/solution interfaces.

Tailored glycosylated anode surfaces: Addressing the exoelectrogen bacterial community via functional layers for microbial fuel cell applications

Grafting of aryldiazonium cations bearing a p-mannoside functionality over microbial fuel cell (MFC) anode materials was performed to investigate the ability of aryl-glycoside layers to regulate colonisation by biocatalytic biofilms. Covalent attachment was achieved via spontaneous reactions and via electrochemically-assisted grafting using potential step experiments. The effect of different functionalisation protocols on MFC performance is discussed in terms of changes in wettability, roughness and electrochemical response of modified electrodes. Water contact angle measurements (WCA) show that aryl-mannoside grafting yields a significant increase in hydrophilic character. Surface roughness determinations via atomic force microscopy (AFM) suggest a more disordered glycan adlayer when electrografting is used to facilitate chemisorption. MFCs were used as living sensors to successfully test the coated electrodes: the response of the MFCs in terms of start-up time was accelerated when compared to that of MFC equipped with non-modified electrodes, this suggests a faster development of a mature biofilm community resulting from aryldiazonium modifications, as confirmed by cyclic voltammetry of MFC anodes. These results therefore indicate that modification with glycans offers a bioinspired route to accelerating biofilm colonisation without any adverse effects on final MFC outputs.

In Situ Scanning Tunneling Microscopy of Cobalt-Phthalocyanine-Catalyzed CO2 Reduction Reaction.

We report a molecular investigation of a cobalt phthalocyanine (CoPc)-catalyzed CO2 reduction reaction by electrochemical scanning tunneling microscopy (ECSTM). An ordered adlayer of CoPc was prepared on Au(111). Approximately 14 % of the adsorbed species appeared with high contrast in a CO2 -purged electrolyte environment. The ECSTM experiments indicate the proportion of high-contrast species correlated with the reduction of CoII Pc (-0.2 V vs. saturated calomel electrode (SCE)). The high-contrast species is ascribed to the CoPc-CO2 complex, which is further confirmed by theoretical simulation. The sharp contrast change from CoPc-CO2 to CoPc is revealed by in situ ECSTM characterization of the reaction. Potential step experiments provide dynamic information for the initial stage of the reaction, which include the reduction of CoPc and the binding of CO2 , and the latter is the rate-limiting step. The rate constant of the formation and dissociation of CoPc-CO2 is estimated on the basis of the in situ ECSTM experiment.

Electrochemical Analysis of the Mechanism of Potassium‐Ion Insertion into K‐rich Prussian Blue Materials

AbstractThe electrochemical insertion patterns of potassium‐rich Prussian blue (PB) materials with different compositions and particle sizes were systematically compared, which allows us to deduce correlations between the influence of particle morphology and material structure on the potassium‐ion insertion mechanisms in aqueous solutions. Although structural analysis indicates that no first‐order phase transitions occur for nanosized K‐rich Prussian blue particles upon potassium‐ion (de)insertion, the electrochemical data (galvanostatic charge/discharge, cyclic voltammetry, small‐ and large‐amplitude potential step experiments) suggest other outcomes related to the two‐phase insertion mechanism for all explored PB samples. However, even in a case whereby the phase transformation is not accompanied by abrupt changes in the crystal structure, the two‐phase mechanism dominates all of the essential practical characteristics of performance of this cathode material, such as hysteresis (overpotential) between charge and discharge steps and the measured diffusivities of potassium‐ions during charge and discharge. The formalism presented herein provides a basis for quantitatively assessing ion insertion and deinsertion parameters unique to PB analogues.

Near Infrared Electrochemiluminescence of Rod-Shape 25-Atom AuAg Nanoclusters That Is Hundreds-Fold Stronger Than That of Ru(bpy)3 Standard.

Near infrared (near-IR) electrogenerated chemiluminescence (ECL) from rod-shape bimetallic Au12Ag13 nanoclusters is reported. With ECL standard tris(bipyridine)ruthenium(II) complex (Ru(bpy)3) as reference, the self-annihilation ECL of the Au12Ag13 nanoclusters is about 10 times higher. The coreactant ECL of Au12Ag13 is about 400 times stronger than that of Ru(bpy)3 with 1 mM tripropylamine as coreactants. Voltammetric analysis reveals both oxidative and reductive ECLs under scanning electrode potentials. Transient ECL signals (tens of milliseconds) and decay profiles are captured by potential step experiments. An extremely strong and transient self-annihilation ECL is detected by activating LUMO and HOMO states sequentially via electrode reactions. The ECL generation pathways and mechanism are proposed based on the key anodic and cathodic activities arising from the energetics of this unique atomic-precision bimetallic nanocluster. Successes in the generation of the unprecedented strong near-IR ECL strongly support our prediction and choice of this nanocluster based on its record-high 40% quantum efficiency of near-IR photoluminescence. Correlation of the properties to the atomic/electronic structures has been a long-pursued goal particularly in the fast growing atomic-precision nanoclusters field. The mechanistic insights provided in this fundamental study could guide the design and syntheses of other nanoclusters or materials in general to achieve improved properties and further affirm the structure-function correlations. The high ECL signal in the less interfered near-infrared spectrum window offers combined merits of high-signal-low-noise/interference or high contrast for broad analytical sensing and immunoassays and other relevant applications.

A novel DEMS approach for studying gas evolution at battery-type electrode|electrolyte interfaces: High-voltage LiNi0.5Mn1.5O4 cathode in ethylene and dimethyl carbonate electrolytes

Aiming at a better molecular scale understanding of electrolyte degradation processes at electrode|electrolyte interfaces typical for modern batteries, in particular for lithium ion batteries (LIBs), we have developed a novel Differential Electrochemical Mass Spectrometry (DEMS) approach, and applied this for analyzing the evolution of volatile decomposition products at a high voltage LiNi0.5Mn1.5O4 (LNMO) cathode. Using a standard LP30 lithium ion battery electrolyte as well as 1.0 M LiPF6 in either ethylene carbonate (EC) or dimethyl carbonate (DMC), respectively, the gas evolution rates during potentiodynamic cycling and in potential step experiments were monitored online, with high time resolution, in half-cell measurements. Following the potential and time dependent appearance of the reaction products and their fragments, the major gases evolved were identified as H2, CO2 and CO. Their formation at the LNMO electrode at high potentials is explained by Ni4+ catalyzed dehydrogenation of organic carbonates, as evidenced in the potential step experiments from the correlation of the charge passed and the continuous gas formation even after decay of current down to zero. Differences in the potential dependent and in the time dependent product formation rates in the three electrolytes point to a non-additive behavior of the solvents EC and DMC in LP30. The results clearly illustrate the potential of this set-up for detailed studies of electrolyte degradation processes in modern battery systems.

Electrochemical Real-Time Mass Spectrometry (EC-RTMS): Monitoring Electrochemical Reaction Products in Real Time.

Methods that provide real-time information are essential to resolve transients occurring at dynamic interfaces. Now a powerful method is presented that enables the time- and potential-resolved characterization of liquid and gaseous products of electrochemical reactions shortly after their formation. To demonstrate its extraordinary potential, the electrochemical real time mass spectrometry (EC-RTMS) approach is used to determine the products of the CO2 reduction reaction (CO2 RR) during potential step or sweep experiments on pristine and in situ anodized copper. The enhanced formation of several C2+ products over C1 products is tracked directly after copper anodization, with unprecedented temporal resolution. This new technique creates exciting new opportunities for resolving processes that occur at short timescales and eventually for guiding the design of new, robust catalysts for selective electrosynthesis under dynamic operation.

Phospholipid bilayers at the mercury (Hg)/water interface

This study reports on the electrochemical characterisation of dioleoyl phospatidylcholine (DOPC) bilayer structures on a negatively polarised mercury (Hg) electrode. The bilayers are stable on the Hg surface between −1.0 and −1.3 V applied potential. The experimental approaches were:- (i) rapid cyclic voltammetry (RCV) to “fingerprint” the bilayers, (ii) potential step experiments to record Zn2+ reduction and, (iii) electrochemical impedance. The results show the following. Both the specific capacitance (5 μF cm−2) and the specific resistance of the bilayer are higher and lower respectively than that of a defect-free free standing DOPC bilayer. This indicates the presence of water and ions in the bilayer within an applied negative field. The bilayer's resistance to electrolyte movement decreases with increase in negative potential to a minimum at −1.3 V. The DOPC bilayer is less permeable to Zn2+ ions compared to the DOPC monolayer coated electrode at applied negative potentials and its permeability to Zn2+ increases with an increase in negative applied potential. The specific capacitance of the bilayer increases to about 7.5 μF cm−2 with increase in applied negative potential showing the increasing significance of water in the bilayer commensurate with its increased permeability to ions. Adsorption of SiO2 nanoparticles on the bilayer surface causes a step negative potential shift in the anodic capacitance current bilayer reformation peak indicating an acceleration of the bilayer reformation process.

Characterization of the Ionic Liquid/Electrode Interfacial Relaxation Processes Under Potential Polarization for Ionic Liquid Amperometric Gas Sensor Method Development.

Electrochemical amperometric sensors require a constant or varying potential at the working electrode that drives redox reactions of the analyte for detection. The interfacial redox reaction(s) can result in the formation of new chemical products that could change the initial condition of the electrode/electrolyte interface. If the products are not inert and/or cannot be removed from the system such that the initial condition of the electrode/electrolyte interface cannot be restored, the sensor signal baseline would consequently drift, which is problematic for the continuous and real-time sensors. By setting the electrode potential with the periodical ON-OFF mode, electrolysis can be forestalled during the off mode which can minimize the sensor signal baseline drift and reduce the power consumption of the sensor. However, it is known that the relaxation of the structure in the electrical double layer at the ionic liquid/electrode interface to the steps of the electrode potential is slow. This work characterized the electrode/electrolyte interfacial relaxation process of an ionic liquid based electrochemical gas (IL-EG) sensor by performing multiple potential step experiments in which the potential is stepped from an open circuit potential (OCP) to the amperometric sensing potential at various frequencies with different time periods. Our results showed that by shortening the sensing period as well as extending the idle period (i.e., enlarge the ratio of idle period versus sensing period) of the potential step experiments, the electrode/electrolyte interface is prone to relax to its original state, and thus reduces the baseline drift. Additionally, the high viscosity of the ionic liquids is beneficial for electrochemical regeneration via the implementation of a conditioning step at zero volts at the electrode/electrolyte. By setting the working electrode at zero volts instead of OCP, our results showed that it could further minimize the baseline drift, enhance the sensing signal stability, and extend the functioning lifetime of a continuous IL-EG oxygen sensor.

Understanding the Hydrogen and Oxygen Evolution Reactions through Microkinetic Models

Micro-kinetic models for hydrogen and oxygen evolution reactions are developed. From these it is shown that the traditional approach involving the use of the quasi-equilibrium assumption can fail to predict the correct electrode behaviour. Using these models, it is also shown that identical polarisation curves can be generated from multiple sets of kinetic parameters. Clearly, a steady-state polarisation curve is insufficient to completely characterize an electrodes kinetics. However, by simulating dynamic electrode response (e.g. a potential step experiment), differences in behaviour between the sets of kinetic parameters can be observed.