The past two decades have seen a renewed and rapidly growing interest in the fields of electrochemistry and electrocatalysis. This is on the one hand stimulated by applications in energy conversion and energy storage, where highly efficient electrochemical or electrocatalytic processes are considered to be an indispensable part of modern energy concepts based on the use of renewable energy sources. However, it is also pushed by the rapid development of modern in situ spectroscopy and microscopy tools as well as the enormous progress that has been made in the theoretical description of processes occurring at the electrochemical solid–liquid interface. This Thematic Series provides a broad perspective covering a variety of important topics in modern electrocatalysis research, with a clear focus on the nanoscale understanding of the relevant processes.
See also the Thematic Series:
Photocatalysis
Scheme 1: Reaction pathways proposed for the ORR given by Wroblowa et al. [1].
Figure 1: Stable voltammetric profile of a well-ordered Pt(111) electrode at 50 mV·s−1, at two upper potentia...
Figure 2: Evolution of the voltammetric profile of a Pt(111) electrode in 0.5 M H2SO4 as the electrode is cyc...
Figure 3: Oxygen reduction on a Pt(111) electrode in oxygen saturated 0.1 M HClO4. (A): Cyclic voltammetric p...
Scheme 2: Possible adlayer reactions.
Scheme 3: Associative ORR mechanism.
Scheme 4: Dissociative ORR mechanism.
Figure 4: Potential free energy diagram for oxygen reduction over Pt(111), Pt(211), Pt(100) and Pt(110) at 0....
Figure 5: Plot of the half-height potential, E1/2, for the oxygen reduction as a function of the angle of the...
Figure 6: Plot of the kinetic currents at 0.8 V, jkin(0.8 V), for the oxygen reduction as a function of the a...
Figure 7: (A) Cyclic voltammograms for the ORR on a hanging meniscus rotating disc (HMRD) Pt(111) electrode f...
Figure 8: Cyclic voltammograms in the high potential region for the ORR on a HMRD Pt(111) electrode in oxygen...
Scheme 5: Reduction and oxidation of hydrogen peroxide.
Figure 9: Hydrogen peroxide reduction and oxidation reactions on Pt(111) in 0.1 M HClO4 + 1 mM H2O2. (A) Cycl...
Figure 1: Simplified representation of suggested degradation mechanisms for platinum particles on a carbon su...
Figure 2: A) ORR cyclic voltammograms of Pt@HGS 1–2 nm in 0.1 M HClO4 saturated with Ar (black) and with oxyg...
Figure 3: Electrochemical oxidation of a carbon monoxide monolayer (CO-stripping curves) after 0, 360, 1080, ...
Figure 4: IL-SEM of Pt/Vulcan 3–4 nm (green), Pt@HGS 1–2 nm (blue) and Pt@HGS 3–4 nm (red) after 0 (top) and ...
Figure 5: Identical location dark field IL-STEM of Pt/Vulcan 3–4 nm (green), Pt@HGS 1–2 nm (blue) and Pt@HGS ...
Figure 6: IL-TEM micrographs of Pt/Vulcan 3–4 nm after 0 and after 3600 potential cycles between 0.4 and 1.4 V...
Figure 7: IL-TEM micrographs of the Pt/Vulcan 3–4 nm catalyst before and after 5000 potential cycles between ...
Figure 8: IL-TEM micrographs of the Pt@HGS 3–4 nm catalyst before and after 5000 potential cycles between 0.4...
Figure 9: IL-TEM micrographs from degradation studies on four Pt/C fuel cell catalysts. Pt/C 5 nm (A,B) and P...
Figure 10: IL-TEM micrograph of Pt/C 5 nm subjected to 1.3 VRHE at 348 K (75 °C) for 16 h in 0.1 M HClO4. A sh...
Figure 11: A) Dependence of the AID on platinum content for various platinum particle sizes, calculated for a ...
Figure 12: Impact of catalyst particle size and post-synthesis heat treatment on the normalized platinum surfa...
Figure 1: (a) Adsorption of oxygen at a nitrogen vacancy site on Mo13N10, and (b) adsorption of oxygen at a n...
Figure 2: The total free energy for covering the Mo13 nanocluster with nitrogen, oxygen or hydrogen. The fill...
Figure 3: (a) The Mo13O6 nanocluster, (b) the Mo13O9 nanocluster with N2 adsorbed, (c) the Mo13O12 with an al...
Figure 4: Diagram of the required applied potential to make each reaction step exergonic for electrochemical ...
Figure 5: Diagram of the required applied potential to make each reaction step exergonic for electrochemical ...
Figure 1: 4D SF/CD-SECM for the investigation of the catalytic activity towards oxygen reduction. a) Scheme o...
Figure 2: a) Scheme of a microcavity used as platform for catalyst immobilisation in cd-mode SECM investigati...
Figure 3: 4D SF/CD-SECM experiment at a partly filled microcavity. a) Optical micrograph with a scheme of the...
Figure 4: Concept of the 4D SF/CD-RC-SECM. Similar to the 4D SF/CD mode the tip is positioned within the shea...
Figure 5: 4D SF/CD-RC-SECM experiment at a 100 µm diameter Pt disk electrode as model sample for an ORR catal...
Figure 6: 4D SF/CD-RC-SECM experiment at a microcavity filled with a Pt/C model catalyst. Topography image a)...
Figure 1: The figures show the relaxed structures of different coverages of chlorine on a Pt(111) surface.
Figure 2: Calculated change of the work function vs coverage for the adsorption of fluorine, chlorine, bromin...
Figure 3: Charge density difference Δλ(z) for the adsorption of fluorine, chlorine, bromine, and iodine on Pt...
Figure 4: Calculated work function versus dipole moment. The solid line corresponds to the expectation accord...
Figure 5: Calculated normalized dipole moment as a function of the coverage of fluorine, chlorine, bromine an...
Figure 6: Contributions to the total dipole moment change Δμ according to Equation 6 and Equation 7 as a function of halogen cove...
Figure 7: Cross sections of electron density difference ρdiff(r) at the surface. Solid-blue (dashed-red) cont...
Figure 1: (a) Representative structure for a model of a hydroxylated inter-grain interface comprising ZrO(OH)2...
Figure 2: The diagram on the left is identical to Figure 1d. The enlarged region exposes the overpotentials for the el...
Figure 3: HER at electro-catalyst/electrode assembly. (A) Coalescence of proton and electrons to form the met...
Figure 1: Evolution of the number of electrons with the number of iterations for O2 if the potential dependen...
Figure 2: Change of the absolute potential for O2 depending on the number of electrons, calculated numericall...
Figure 3: Chemical potential of the O2 molecule, plotted against the number of electrons, calculated numerica...
Figure 4: Scheme for a potential dependent calculation of the free energy.
Figure 5: Convergence of the number of electrons with the SCF iterations for different systems. Note that the...
Figure 1: Left: Hydrogen-region voltammograms recorded at 50 mV s−1 in 0.5 M H2SO4. Black, green and red trac...
Figure 2: Comparison of the anodic scan of the hydrogen-region voltammograms recorded in the beaker cell (col...
Figure 3: IR vibrational spectra of irreversibly adsorbed CO recorded at 0.10 V (left panel) and of adsorbed ...
Figure 4: First (solid lines) and second (dashed lines) positive going scans of CO stripping voltammograms (a...
Figure 5: Normalized mass spectrometric current (m/z = 44, CO2 detection, red dotted line) and Faradaic curre...
Figure 6: Plots of the currents from (bi)sulfate anions re-adsorption (colored traces), absolute COad coverag...
Figure 1: Temporal evolution of the ATR-FTIR spectra upon admission of 0.1 M H2- or D2-formaldehyde solution ...
Figure 2: Initial ATR-FTIR spectra acquired ca. 2 s after admission of 0.1 M H2- or D2-formaldehyde solution ...
Figure 3: Transients of Faradaic current (upper panel) and integrated intensities of linearly bonded COad (mi...
Figure 4: Initial COad formation rates (a) and kinetic isotope effects for the COad formation (b) upon admiss...
Figure 1: Trassati’s volcano plot for the hydrogen evolution reaction in acid solutions. j00 denotes the exch...
Figure 2: ’Volcano’ plots for hydrogen evolution in acid and alkaline aqueous solutions. Note that ascending ...
Figure 3: Square of the coupling constants between the H1s orbital and the d bands of Pt(111), Ni(111), Cu(11...
Figure 4: Densities of states of the d bands of Ni(111) and of the 1s spin orbitals of a hydrogen atom at a d...
Figure 5: Free energy surface for the Volmer reaction on Ni(111) in acid solution at the equilibrium potentia...
Figure 6: Oxygen reduction on various substrates in acid solutions. Left: logarithm of the current at 800 mV ...
Figure 1: Snapshot for a water film with two adsorbed Cl− ions (green).
Figure 2: Distribution of discharge times (represented as probabilities to observe discharge within a 5 ps ti...
Figure 3: Average proton distance from the metal surface zH as a function of time for pure water (red squares...
Figure 4: Average proton distance from the metal surface zH as a function of time for pure water (red squares...
Figure 5: Lateral proton positions at the instant of discharge marked as red × symbols (left) and probability...
Figure 6: Cumulative probability to observe proton discharge within a radius r around the Na+ ion (red) and t...
Figure 1: Cyclic voltammograms of Ir(210), which was annealed and cooled in a N2 + CO mixture, after anodic s...
Figure 2: (a) in situ STM image of CO-cooled Ir(210) in 0.1 M H2SO4 at −0.2 V. (b) Height profile along the l...
Figure 3: in situ STM image of H2-cooled Ir(210) in 0.1 M H2SO4 at 0.35 V. (b) Height profile along the line ...
Figure 4: Current–potential curves for Ir(210) in 0.1 M H2SO4 after cycling at 1 V·s−1 between −0.28 and 0.7 ...
Figure 5: Current densities for hydrogen adsorption peaks of Ir(210) in 0.1 M H2SO4 as a function of the pote...
Figure 6: In situ STM images (100 × 100 nm2) of CO-cooled Ir(210) surface in 0.1 M H2SO4 after cycling betwee...
Figure 7: Height profiles of the CO-cooled Ir(210) surface in 0.1 M H2SO4 after cycling between −0.28 and 0.7...
Figure 8: Current–potential curves for CO adlayer oxidation on Ir(210) in 0.1 M H2SO4 before and after changi...