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A novel electrochemical cell design in a vertically stacked configuration is presented. Through a layered structure using a top macroporous working electrode, a polyelectrolyte, and a bottom metallic conductor a standalone electrochemical cell with an internal reference electrode is built. This sensor allows monitoring an electrochemical property of an external solution with only one electrode in direct contact with the sample. Using paper-based platinum electrode for the porous top electrode and Nafion as polyelectrolyte material, the self-powered detection of hydrogen peroxide is performed. The system can be operated in multiple modes. In a capacitive way, the open circuit potential is measured. Alternatively, in a self-powered current mode, the system emulates a fuel cell. Additionally, a potential-current switched mode is also demonstrated. Because of this unique design and operational features this sensor is considered as an electrochemical pixel. To further demonstrate the advantages of this device, the detection of glucose is performed by building an array of sensors using a single back (reference) electrode and multiple working electrodes. These results lay the groundwork for the development of a new generation of simple and low cost biochemical sensors and electrochemical sensing arrays.Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.

The oxygen reduction reaction was investigated at 10 monolayers (MLs) of Pt electrodeposited on (Nb–Ti)2AlC substrate. Following the discussion of detailed kinetics and electrodeposition optimisation in the authors’ previous paper, the focus of this research was on stability testing. Previously performed optimisation results showed the best activity shown by 10 monolayers of Pt. Catalyst characterisation was performed by scanning electron microscopy, X-ray photoelectron spectroscopy and transmission electron microscopy. SEM, EDS and XPS analysis showed that the surface was covered with a homogeneous layer of Pt. TEM analysis of a cross-section confirmed the presence of Pt layer of thickness ∼3.5 nm, corresponding to the 10 MLs of Pt. Although the mass activity for the ORR at 0.8 V vs. RHE of 37.4 A g−1 was comparable with the best one for the Pt/C benchmark, US Department of Energy Protocols revealed excellent catalyst stability – the loss of electrochemically active surface area (EASA) was found to be only 9.3%.

The impact of the pH on the corrosion of microporous nickel-chromium coatings has been explored at localised scale by Scanning Electrochemical Microscopy and validated by potentiodynamic polarisation measurements. Results not only reveal the correlation between both techniques but also enables to identify the different corrosion rate after increasing the electrolyte aggressiveness varying the pH. However, independently of the pH, a similar corrosion mechanism was determined: the cross-section micrographs (by Field Emission-Scanning Electron Microscope) have revealed an isotropic growth of the actives sites at early-stage corrosion as well as the attack of different nickel layers during the corrosion propagation., Green Open Access added to TU Delft Institutional Repository 'You share, we take care!' - Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public., Team Yaiza Gonzalez Garcia

Electrolyte effects play an important role in the activity of the oxygen reduction reaction (ORR) of Pt-based electrodes. Herein, we combine a computational model and rotating disk electrode measurements to investigate the effects from phosphate anion poisoning for the ORR on well-defined extended Pt surfaces. We construct a model including the poisoning effect from phosphate species on Pt(111) and Cu/Pt(111) based on density functional theory simulations. By varying the subsurface Cu content of the Cu/Pt(111) alloy, we tune the *OH binding energies on the surface by means of ligand effects, and as a result, we tune the ORR activity. We have investigated the effect of adsorbed phosphate species at low overpotentials when tuning *OH binding energies. Our results display a direct scaling relationship between adsorbed *OH and phosphate species. From the model, we observe how the three-fold binding sites of phosphate anions limit the packing of poisoning phosphate on the surface, thus allowing for *OH adsorption even when poisoned. Our work shows that, regardless of surface site blockage from phosphate, the trend in the catalytic oxygen reduction activity is predominantly governed by the *OH binding.

Manganese oxide nanowires (MONW) combined with carbon nanostructures were synthesized using three different carbon materials, and their effect on the activity towards Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) was investigated in alkaline electrolytes. The carbon structures were carbon nanofibers (CNF), multiwall carbon nanotubes (CNT) and reduced graphene oxide (rGO). Both MONW and carbon nanostructures were characterized by X-ray diffraction, scanning and transmission electron microscopy, N2 physisorption and X-ray photoelectron spectroscopy. The electrochemical activity was assessed in a three-electrode cell. Composite MONW/CNF showed the best activity towards ORR, and MONW/rGO exhibited the highest activity towards OER of the series. The addition of the carbon nanostructures to MONW increased the number of electrons transferred in the ORR, indicating a synergistic effect between the carbon and manganese oxide structures due to changes in the reaction pathway. The analysis of Tafel slopes and electrochemical impedance spectroscopies showed that carbons and MONW catalyze different steps of the reactions, which explains the better activity of the composites. This led us to synthesize a MONW/rGO-CNF composite, where rGO-CNF is a hybrid carbon material. Composite MONW/rGO-CNF showed an improved activity towards ORR, close to the benchmark Pt/C catalyst, and activity towards OER, close to MONW/rGO, and better than the benchmark IrO2 catalyst. It also showed remarkable stability in challenging operation conditions.

The search for better and cheaper electrocatalysts is vital in the global transition to renewable energy resources. High-entropy alloys (HEAs) provide a near-infinite number of different alloys with approximately continuous properties such as catalytic activity. In this work, the catalytic activity for the electrochemical oxygen reduction reaction as a function of molar composition of Ag-Ir-Pd-Pt-Ru HEA is treated as a landscape wherein it is shown that the maxima are connected through ridges. By following the ridges, it is possible to navigate between the maxima using a modified nudged elastic band (NEB) model integrated in a machine learning NEB algorithm. These results provide a new understanding of the composition space being similar to an evolutionary landscape. This provides a possible new search and design strategy for new catalysts in which the composition of known catalysts can be optimized by following ridges rather than exploring the whole alloy composition space.

ZIF8 without and with adsorption of minor amounts of Co precursor have been pyrolized at different temperatures studying systematically the effect of carbonization temperature on the texture, composition and ORR performance both in acidic and basic media. The increase of pyrolysis temperature diminished the N content but increased the graphitic character. The trade-off between these two parameters in metal-free electrocatalysts resulted in an improvement of ORR performance, which is met for the highest pyrolysis temperature of 1000 ºC. Moreover, the adsorption of minor amount of Co precursor enhanced further the ORR performance, increased the graphitic character and the porosity of the resulting carbon material. Morphologically, these carbon materials kept the polyhedral shape of ZIF8 and were covered by graphitic nanostructures devoid of metal nanoparticles. Co metal catalysed the growth of these graphitic nanostructures and concomitantly is stabilized as monoatomic Co-Nx-C species preventing the agglomeration as metal nanoparticles. Therefore, the need of an acid washing step is avoided, which is usually necessary in the carbonization of other metal containing MOFs.

Iron(II) phthalocyanines (FePc) supported on functionalized nanostructured carbon materials have been studied as electrocatalysts for the oxygen reduction reaction (ORR) in an alkaline medium. Herein, two types of carbon nanotubes (CNTs) have been explored as support, Single-Walled Carbon Nanotubes and Herringbone Carbon Nanotubes (SWCNTs and hCNTs, respectively), both electrochemically modified with ortho- aminophenylphosphonic acid (2APPA), which provides phosphate axial coordinating ligands for the immobilization of FePc molecules. All the catalysts were prepared via a facile incipient wetness impregnation method. Comprehensive experimental analysis together with density functional theory (DFT) calculations has demonstrated both the importance of the five-coordinated Fe macrocycles that favor the interaction between the FePc and the carbon support, as well as the effect of the CNT structure in the ORR. FePc axial coordination provides a better dispersion, leading to higher stability and a favorable electron redistribution that also tunes the ORR performance by lowering the stability of the reaction intermediates. Interestingly, such improvement occurs with a very low content of metal (∼1 wt% Fe), which is especially remarkable when hCNT support is employed. This work provides a novel strategy for the development of Fe-containing complexes as precious metal-free catalysts towards the ORR.

Upon the electrochemical reduction of an in situ generated 5-diazo-1,10-phenanthroline ion, phenanthroline was covalently attached to a gold electrode. The grafted molecules act as a ligand when brought in contact with a copper-containing electrolyte solution. As the ligands are limited in spatial movement, the exclusive formation of the active species with only one phenanthroline ligand coordinated was expected. The in situ generated complexes have been investigated for activity in the oxygen reduction reaction, for which an overpotential of 800 mV is observed. During catalysis, initially a thick copper layer is formed on top of an organic layer that is still present on the gold surface. Upon deterioration of the organic layer underneath the copper over time, the amount of copper on the electrode and thereby the electrocatalytic activity decreases.

Hydrogen peroxide (H2O2) is an important chemical as it is an environmentally friendly oxidant for organic synthesis and environmental remediation as well as a promising candidate for the liquid fuel. Photocatalytic generation of H2O2 is sustainable, and many efforts have been put into the development of new catalysts to gain high H2O2 yields. In this investigation, Au/ZnO, Ag/ZnO and Au-Ag/ZnO catalysts were prepared by the simultaneous impregnation of HAuCl4 and AgNO3 and they were used to generate H2O2 from a methanol/O2 system. It was demonstrated that Au/ZnO had the best performance at generating H2O2. The presence of Au on ZnO accelerated the generation of H2O2 on ZnO and facilitated H2O2 adsorption onto the catalyst surface, which resulted in the reaction kinetics changing from zero-order to first-order. Ag atoms on Ag/ZnO were unstable and would strip from the surface of ZnO during irradiation, decreasing the yield of H2O2. The stabilization of Ag on Au-Ag/ZnO depended on the ratio of Au and Ag. Au0.1Ag0.2/ZnO was a stable catalyst and it showed that the presence of Ag promoted the formation and decomposition of peroxide, simultaneously.

Potential applications of 2D metal-organic frameworks (MOF) require the frameworks to be monophase and well-defined at the atomic scale, to be decoupled from the supporting substrate, and to remain stable at the application conditions. Here,we present three systems meeting this elusive set of requirements: M-TCNQ (M = Ni, Fe, Mn) on epitaxial graphene/Ir(111). We study the systems experimentally by scanning tunneling microscopy, low energy electron microscopy and x-ray photoelectron spectroscopy. When synthesized on graphene, the 2D M-TCNQ MOFs are monophase with M1(TCNQ)1 stoichiometry, no alternative structure was observed with slight variation of the preparation protocol. We further demonstrate a remarkable chemical and thermal stability of TCNQ-based 2D MOFs: All the studied systems survive exposure to ambient conditions, with Ni-TCNQ doing so without any significant changes to its atomic-scale structure or chemical state. Thermally, the most stable system is Fe-TCNQ which remains stable above 500 °C, while all the tested MOFs survive heating to 250 °C. Overall, the modular M-TCNQ/graphene system combines the atomic-scale definition required for fundamental studies with the robustness and stability needed for applications, thus we consider it an ideal model for research in single atom catalysis, spintronics or high-density storage media.

Potential applications of 2D metal-organic frameworks (MOF) require the frameworks to be monophase and well-defined at the atomic scale, to be decoupled from the supporting substrate, and to remain stable at the application conditions. Here,we present three systems meeting this elusive set of requirements: M-TCNQ (M = Ni, Fe, Mn) on epitaxial graphene/Ir(111). We study the systems experimentally by scanning tunneling microscopy, low energy electron microscopy and x-ray photoelectron spectroscopy. When synthesized on graphene, the 2D M-TCNQ MOFs are monophase with M1(TCNQ)1 stoichiometry, no alternative structure was observed with slight variation of the preparation protocol. We further demonstrate a remarkable chemical and thermal stability of TCNQ-based 2D MOFs: All the studied systems survive exposure to ambient conditions, with Ni-TCNQ doing so without any significant changes to its atomic-scale structure or chemical state. Thermally, the most stable system is Fe-TCNQ which remains stable above 500 °C, while all the tested MOFs survive heating to 250 °C. Overall, the modular M-TCNQ/graphene system combines the atomic-scale definition required for fundamental studies with the robustness and stability needed for applications, thus we consider it an ideal model for research in single atom catalysis, spintronics or high-density storage media.

Potential applications of 2D metal-organic frameworks (MOF) require the frameworks to be monophase and well-defined at the atomic scale, to be decoupled from the supporting substrate, and to remain stable at the application conditions. Here,we present three systems meeting this elusive set of requirements: M-TCNQ (M = Ni, Fe, Mn) on epitaxial graphene/Ir(111). We study the systems experimentally by scanning tunneling microscopy, low energy electron microscopy and x-ray photoelectron spectroscopy. When synthesized on graphene, the 2D M-TCNQ MOFs are monophase with M1(TCNQ)1 stoichiometry, no alternative structure was observed with slight variation of the preparation protocol. We further demonstrate a remarkable chemical and thermal stability of TCNQ-based 2D MOFs: All the studied systems survive exposure to ambient conditions, with Ni-TCNQ doing so without any significant changes to its atomic-scale structure or chemical state. Thermally, the most stable system is Fe-TCNQ which remains stable above 500 °C, while all the tested MOFs survive heating to 250 °C. Overall, the modular M-TCNQ/graphene system combines the atomic-scale definition required for fundamental studies with the robustness and stability needed for applications, thus we consider it an ideal model for research in single atom catalysis, spintronics or high-density storage media.

Potential applications of 2D metal-organic frameworks (MOF) require the frameworks to be monophase and well-defined at the atomic scale, to be decoupled from the supporting substrate, and to remain stable at the application conditions. Here,we present three systems meeting this elusive set of requirements: M-TCNQ (M = Ni, Fe, Mn) on epitaxial graphene/Ir(111). We study the systems experimentally by scanning tunneling microscopy, low energy electron microscopy and x-ray photoelectron spectroscopy. When synthesized on graphene, the 2D M-TCNQ MOFs are monophase with M1(TCNQ)1 stoichiometry, no alternative structure was observed with slight variation of the preparation protocol. We further demonstrate a remarkable chemical and thermal stability of TCNQ-based 2D MOFs: All the studied systems survive exposure to ambient conditions, with Ni-TCNQ doing so without any significant changes to its atomic-scale structure or chemical state. Thermally, the most stable system is Fe-TCNQ which remains stable above 500 °C, while all the tested MOFs survive heating to 250 °C. Overall, the modular M-TCNQ/graphene system combines the atomic-scale definition required for fundamental studies with the robustness and stability needed for applications, thus we consider it an ideal model for research in single atom catalysis, spintronics or high-density storage media.

Motivated by the recent experimental discovery of C6N7 monolayer (Zhao et al 2021 Science Bulletin 66, 1764), we show that C6N7 monolayer co-doped with C atom is a Dirac half-metal by employing first-principle density functional theory calculations. The structural, mechanical, electronic and magnetic properties of the co-doped C6N7 are investigated by both the PBE and HSE06 functionals. Pristine C6N7 monolayer is a semiconductor with almost isotropic electronic dispersion around the Gamma point. As the doping of the C6N7 takes place, the substitution of an N atom with a C atom transforms the monolayer into a dilute magnetic semiconductor, with the spin-up channel showing a band gap of 2.3 eV, while the spin-down channel exhibits a semimetallic phase with multiple Dirac points. The thermodynamic stability of the system is also checked out via AIMD simulations, showing the monolayer to be free of distortion at 500 K. The emergence of Dirac half-metal in carbon nitride monolayer via atomic doping reveals an exciting material platform for designing novel nanoelectronics and spintronics devices., National Research Foundation of Korea (NRF) - Korea government (MSIT) [NRF-2017R1A2B2011989], This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (NRF-2017R1A2B2011989).

Motivated by the recent experimental discovery of C6N7 monolayer (Zhao et al 2021 Science Bulletin 66, 1764), we show that C6N7 monolayer co-doped with C atom is a Dirac half-metal by employing first-principle density functional theory calculations. The structural, mechanical, electronic and magnetic properties of the co-doped C6N7 are investigated by both the PBE and HSE06 functionals. Pristine C6N7 monolayer is a semiconductor with almost isotropic electronic dispersion around the Gamma point. As the doping of the C6N7 takes place, the substitution of an N atom with a C atom transforms the monolayer into a dilute magnetic semiconductor, with the spin-up channel showing a band gap of 2.3 eV, while the spin-down channel exhibits a semimetallic phase with multiple Dirac points. The thermodynamic stability of the system is also checked out via AIMD simulations, showing the monolayer to be free of distortion at 500 K. The emergence of Dirac half-metal in carbon nitride monolayer via atomic doping reveals an exciting material platform for designing novel nanoelectronics and spintronics devices., National Research Foundation of Korea (NRF) - Korea government (MSIT) [NRF-2017R1A2B2011989], This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (NRF-2017R1A2B2011989).

Platinum layers on MAX phases based supports as advanced materials for low temperature fuel cells application NEVENKA R. ELEZOVIC* *University of Belgrade - Institute for Multidisciplinary Research, Kneza Viseslava 1, 11030 Belgrade, Serbia Proton exchange membrane fuel cells (PEMFCs) are considered as promising future environmental friendly power sources. However, before the commercialization some important issues have to be resolved. MAX phase materials, such as Ti2AlC or (Nb-Ti)2AlC have been considered as perspective materials for variety of applications. These materials demonstrated high chemical and corrosion stability, high conductivity – close to metals′ one, as well as excellent stability in a wide potential range when used for electrochemical systems in water solutions. Moreover, commercialization was achieved at a very reasonable price. Thus, above mentioned materials could be promising alternative for catalyst supports in PEMFCs if compared to state-of-the-art carbon based materials. On the other hand, platinum is considered as the best catalyst for both anode and cathode reactions taking place in PEMFCs: hydrogen oxidation and oxygen reduction, especially in acid solutions. Having in mind the high cost and scarcity of Pt, deposition of ultrathin Pt layers on Max phases could be of great practical importance. In this research a facile and cost effective electrochemical method for successful deposition of thin Pt films (up to 10 monolayers) onto Ti2AlC and (Nb-Ti)2AlC substrate was referred. The obtained catalysts were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscpopy (EDS), and X-ray photoelectron spectroscopy (XPS). The oxygen reduction and hydrogen oxidation reactions were investigated by linear sweep voltammetry at rotating disc electrode (RDE). The results confirmed high activity and excellent stability in comparison to commercial carbon based Pt catalyst. Challenges and perspectives of these novel materials f

Pd/GC electrodes were prepared by the electrochemical deposition of palladium on glassy carbon (GC) using PdSO4 or PdCl2 salts. As-prepared GC-supported Pd nanoparticles were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). XPS spectra revealed that the depositing palladium salt anion influences the oxidation state of the deposited Pd, while AFM images showed its effect on Pd nanoparticle size and coverage. The deposition from the PdCl2 salt solution resulted in smaller palladium nanoparticles, but much higher GC surface coverage than from PdSO4. The activity of Pd/GC electrodes towards oxygen reduction was examined in acid and alkaline media using the rotation-disc electrode. Among the different Pd/GC electrodes, the one prepared using PdCl2 salt with the full Pd coverage has shown the best ORR activity. The ORR occurs through a 4e-series reaction mechanism like on polycrystalline palladium but exceeds its activity concerning the initial potential.

The main objective of this research was a systematic development of advanced micro/nanostructured materials based on the most used metal-oxides for ORR and metal-oxides with an extremely low-loading of Pt for comparison. Hybrid composites compared were: MnO2, La2O3, mixed lanthanum manganese oxides (LMO), and mixed lanthanum manganese oxides with reduced platinum load (LMO-Pt). The influence of the reduced amount of noble metal, as well as single oxide activity toward ORR, was analyzed. The complete electrochemical performance of the hybrid materials has been performed by means of CV, LSV, and EIS. It was shown that all synthesized catalytic materials were ORR-active with noticeable reduction currents in O2 saturated 0.1 M KOH. The ORR behavior indicated that the La2O3 electrode has a different mechanism than the other tested electrode materials (MnO2, LMO, and LMO-Pt). The EIS results have revealed that the ORR reaction is of a mixed character, being electrochemically and diffusion controlled. Even more, diffusion is of mixed character due to transport of O2 molecules and the chemical reaction of oxygen reduction. O2 diffusion was shown to be the dominant process for MnO2, LMO, and LMO-Pt electrolytic materials, while chemical reaction is the dominant process for La2O3 electrolytic materials.

The increasing demand of energy that humanity had suffer in the last times, added to the global warming expanse associated to the fossil fuels used as main energy source, have made that the humanity has to afford one of its highest challenges: the search for new sources of sustainable energy. Currently, the use of electrochemical energy conversion systems like fuel cells (FC) and electrolysers (PEM) have been raised as good candidate to solve this problem. These kinds of devices are so important than some government agencies have proposed some strategies in order to develop the use of green H2 as alternative for the generation of electrical energy. In this sense, some strategies like the pickups stabilised by the European Union as “European Green Deal” or “EU Hydrogen Strategy” remarks the importance of contribute to the improvement of these technologies in order to reach a more sustainable future. To accomplish these targets, low temperature unitized regenerative fuel cells (URFC) are a promising technology for storing energy via hydrogen. A URFC consists of a single device capable of working as a FC and WE, in such a way that only one of the modes is operational in time. With these devices is possible to generate hydrogen by the electrolysis of water supplied by renewable energies, its storage and its use directly in the URFC to obtain electricity when necessary. However, development of these technologies has its main limitation in the oxygen electrode reactions, which are the oxygen reduction (ORR) and evolution (OER) reactions, whose high overpotential in both reactions (1.23 V vs RHE) make necessary the use of catalysts based on noble metals which increase significantly the cost of manufacture. To solve this, in the last decade the efforts have been focused in the use of carbon-based materials as catalysts combined with early transition metals, creating a new range of materials named composites, whose high conductivity, availability and stability make them good

High-entropy alloy (HEA) electrocatalysts offer a vast composition space that awaits exploration to identify interesting materials for energy conversion reactions. While attempts have been made to explore the composition space of HEA thin-film libraries and compare experimental and computational studies, no corresponding approaches exist for HEA nanoparticles. So far, catalytic investigations on HEA nanoparticles are limited to small sets of individual catalysts. Here, we report the experimental exploration of the composition space of carbon-supported Pt-Ru-Pd-Rh- Au nanoparticles for the H-2/CO oxidation reaction by constructing a dataset using Bayesian optimization as guidance. Applying a surfactant-free synthesis platform, a dataset of 68 samples was investigated. By constructing machine learning models, the relationship between the concentrations of the constituent elements and the catalytic activity was analyzed and compared to density functional theory calculations. The machine learning models confirm findings from previous studies concerning the role of Ru in the H-2/CO oxidation reaction. This has been achieved starting from a random set of compositions and without any prior assumptions for the reaction mechanism nor any in-depth design of the active site. In addition, by comparing the trends of the computational and experimental studies, it is seen that the "onset potentials " across the compositions can be correlated with the adsorption energy of *OH. The best correlation between the computational and experimental data is obtained when considering 5% of the most strongly *OH adsorbing sites.

Selective partial oxidation of hydrocarbons to oxygenates plays a large role in the chemical industry, while falling prices for electricity from renewable sources make electrification of such industrial chemical processes relevant. The oxidation of propene is an interesting model system as propene can be oxidized in two different positions, allowing for insights into the reaction mechanism. On Pd, a layer of adsorbates formed in situ governs the reaction by steering reactant adsorption to achieve high selectivity for allyl oxidation, albeit largely inhibiting the reaction rate. Through rational catalyst design, we demonstrate that alloying reactive Pd with inert Au influences the adsorbate layer formation, enhancing activity while maintaining high selectivity toward allyl oxidation. We obtain mechanistic insights with a combination of ab initio computational modeling and electrochemical measurements with ex situ product quantification and online mass spectrometry. Using a statistical approach, we explore the correlation of the Au:Pd ratio with Pd surface cluster size and density, which determine the properties of the adsorbate layer and thus the reaction outcome. We report an activity enhancement by a factor 2.4 with 10% Au in Pd and propose that (i) activity is maximized at potentials just before Pd cluster oxidation and (ii) the optimal catalyst surface contains approximately one Au every six Pd atoms, statistically most frequent at the nominal alloy composition Au14Pd86.

Catalytic activity towards the oxygen reduction reaction (ORR) in 0.5 M H2SO4 was investigated at sub-monolayers and ultra-thin layers (corresponding to 10, 30 and 100 monolayers, (MLs)) of Pt electrochemically deposited on (Nb-Ti)2AlC substrate. Electrochemical deposition of Pt layers on (Nb-Ti)2AlC substrate was achieved from the solution containing 3 mM K2PtCl4 + 0.5 M NaCl (pH 4) under the conditions of convective diffusion (RPM = 400) using linear sweep voltammetry (LSV) at a sweep rate of 2 mV s-1, by determining limiting potential for deposition of each Pt sample from the QPt vs. E curves. The Pt samples were characterized X-ray photoelectron spectroscopy (XPS). XPS analysis showed that practically the whole surface of (Nb-Ti)2AlC substrate is covered with homogeneous layer of Pt, while Pt ion reduction was complete to metallic form – Pt(0) valence state. Then oxygen reduction was studied at rotating disc electrode by cyclic voltammetry and linear sweep voltammetry. Two different Tafel slopes were observed, one close to 60 mV dec-1 in low current densities region and second one ~ 120 mV dec-1 in high current densities region. This novel catalyst exhibited higher activity in comparison to carbon supported one, in terms of mass activity – kinetic current density normalized to Pt loading., Ispitivana je reakcija redukcije kiseonika na tankim slojevima platine u 0.5 mol dm-3 H2SO4. Tanki slojevi platine – čija količina naelektrisanja odgovara 10, 30 i 100 teorijskih monoslojeva Pt su istaloženi na nosaču od (Nb-Ti)2AlC. Za elektrohemijsko taloženje je korišćen rastvor 3 mM K2PtCl4 + 0.5 M NaCl pH = 4, u uslovima konvektivne difuzije (RPM = 400) primenom metode linearne skenirajuće voltametrije (LSV) pri brzini promene potencijala od 2 mV s-1 . Elektrohemijski dobijeni platinski katalizatori na pomenutom nosaču su okarakterisani metodom fotoelektronske spektroskopija X-zraka (XPS), kao i elektrohemijskim tehnikama. Za određivanje realne elektrohemijski aktivne površine elektrode je primenjena ciklična voltametrija, integracijom ispod anodnog dela voltamograma u oblasti adsorpcije vodonika na potpotencijalima. Za ispitivanje kinetike reakcije redukcije kiseonika je korišćena metoda linearne skenirajuće voltametrije na rotirajućoj disk elektrodi. Dobijene su dve vrednosti Tafelovog nagiba, jedna približno 60 mV dek-1 u oblasti malih prenapetosti, a druga ~ 120 mV dek-1 , u oblasti većih gustina struje. Katalitička aktivnost katalizatora je poređena sa vrednostima iz literature dobijenim na platini na ugljeničim nosačima na 0.85 V prema reverzibilnoj vodoničnoj elektrodi, izražena kao kinetička gustina struje po realnoj površini electrode, ili specifična aktivnost – izražena kao kinetička gustina struje po masi platine. Pokazano je da katalizator sa 10 monoslojeva platine poseduje veoma dobru katalitičku aktivnost, posebno izraženu po masi istaložene platine.

PdPt bimetallic nanoparticles on carbon-based supports functioning as advanced electrode materials have attracted attention due to their low content of noble metals and high catalytic activity for fuel cell reactions. Glassy carbon (GC)-supported Pt and PdPt nanoparticles, as promising catalysts for the oxygen reduction reaction (ORR), were prepared by the electrochemical deposition of Pt and the subsequent spontaneous deposition of Pd. The obtained electrodes were examined using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM), and electroanalytical techniques. An XPS analysis of the PdPt/GC with the highest ORR performance revealed that the stoichiometric ratio of Pd: Pt was 1:2, and that both Pt and Pd were partially oxidized. AFM images of PdPt2/GC showed the full coverage of GC with PdPt nanoparticles with sizes from 100–300 nm. The ORR activity of PdPt2/GC in an acid solution approached that of polycrystalline Pt (E1/2 = 0.825 V vs. RHE), while exceeding it in an alkaline solution (E1/2 = 0.841 V vs. RHE). The origin of the improved ORR on PdPt2/GC in an alkaline solution is ascribed to the presence of a higher amount of adsorbed OH species originating from both PtOH and PdOH that facilitated the 4e-reaction pathway.

Abstract2D electrode materials are often deployed on conductive supports for electrochemistry and there is a great need to understand fundamental electrochemical processes in this electrode configuration. Here, an integrated experimental-theoretical approach is used to resolve the key electronic interactions in outer-sphere electron transfer (OS-ET), a cornerstone elementary electrochemical reaction, at graphene as-grown on a copper electrode. Using scanning electrochemical cell microscopy, and co-located structural microscopy, the classical hexaamineruthenium (III/II) couple shows the ET kinetics trend: monolayer > bilayer > multilayer graphene. This trend is rationalized quantitatively through the development of rate theory, using the Schmickler-Newns-Anderson model Hamiltonian for ET, with the explicit incorporation of electrostatic interactions in the double layer, and parameterized using constant potential density functional theory calculations. The ET mechanism is predominantly adiabatic; the addition of subsequent graphene layers increases the contact potential, producing an increase in the effective barrier to ET at the electrode/electrolyte interface.

In this work three mesoporous nitrogen-doped carbon support materials were evaluated for oxygen reduction reaction (ORR) in comparison to Vulcan carbon in 0.1 M KOH and 0.5 M H2SO4 solutions. Palladium nanoparticles were synthesised using citrate method and the average particle size of 3.9 ± 0.6 nm was obtained, which was determined from transmission electron microscopy (TEM) images. Unique porosities of these mesoporous engineered catalyst supports (ECS) were evaluated using the BET method and all of the materials displayed similar microporosity, altrough mesopore distribution varied greatly between these materials. Three different loadings of the Pd catalyst were applied to the support materials (varying between 20-40 wt% of Pd) to evaluate the support ability to disperse a large amount of Pd. By comparing the 40 wt% Pd loaded ECS-003604 and Vulcan XC-72R it can be noted that the Vulcan carbon-supported Pd catalyst is more agglomerated. The agglomeration of this catalyst is also noticeable from cyclic voltammetry (CV) studies, where the PdO reduction peak shifts to more positive values as compared to the mesoporous Pd/C counterparts. The ORR kinetics were explored using the rotating disc electrode (RDE) method. In acidic media a Pd catalyst supported on a bimodal mesoporous ECS material showed highest specific activity for oxygen electroreduction, while in alkaline the activity difference is less noticeable between the Pd-based electrocatalyst materials. One of the mesoporous N-doped carbon supported Pd catalyst was also compared to Pd/Vulcan cathode in single-cell alkaline anion exchange membrane fuel cell and improved peak power density was observed.

The photo-/electrocatalysts with high activities for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR) are of significance for the advancement of photo-/electrochemical energy systems such as solar energy to resolve the global energy crisis, reversible water electrolyzers, metal-air batteries, and fuel cells. In the present work, we have systematically investigated the photochemical performance of the 2D beta-antimonene (beta-Sb) monolayer. From density functional theory investigations, beta-Sb with single-atom doping possesses a trifunctional photocatalyst with high energetics and thermal stabilities. In particular, it is predicted that the performance of the HER activity of beta-Sb will be superior to most of the 2D materials. Specifically, beta-Sb with single atom replacement has even superior that the reference catalysts IrO2(110) and Pt(111) with relatively low overpotential values for ORR and OER mechanisms. The superior catalytic performance of beta-Sb has been described by its electronic structures, charge transfer mechanism, and suitable valence and conduction band edge positions versus normal hydrogen electrode. Meanwhile, the low overpotential of multifunctional photocatalysts of the Bi@beta-Sb monolayer makes them show a remarkable performance in overall water splitting (0.06 V for HER, 0.25 V for OER, and 0.31 V for ORR). In general, the Bi@beta-Sb monolayer may be an excellent trifunctional catalyst that exhibits high activity toward all electrode reactions of hydrogen and oxygen.

PdAu/GC nanoparticles obtained by the electrochemical deposition of gold followed by the spontaneous palladium deposition show a remarkable catalytic activity for the oxygen reduction reaction (ORR) in perchloric acid solution. AFM images reveal the size, shape, and coverage of the GC electrode with Au and PdAu nanoislands. Au/GC electrode with the full GC coverage by the deposited gold islands and activated by potential cycling shows the highest ORR activity. The initial potential for ORR shifts positively for 200 mV compared to polycrystalline gold. With the addition of palladium, the activity for ORR enhances significantly. For the most active PdAu/GC electrode, the initial potential shifts positively for another 250 mV, which coincides with polycrystalline palladium.

Stability is an essential metric of electrocatalysts, but the reported experimental results are often flawed, indicated by the highly inconsistent stability data of the reference catalysts seen in the literature. In this work, focusing on the Pt/C reference catalyst toward the oxygen reduction reaction, we attempted to clarify its genuine stability under the most used accelerated stress test conditions and understand the reasons for the flawed results. Efforts have been made to design an electrochemical cell and an extended test protocol to control all possible experimental factors that could influence the test results. We found that simple experimental errors such as incomplete catalyst activation and accumulated electrolyte impurities could significantly affect the stability test results. Under strictly controlled conditions, a reliable stability benchmark of Pt/C catalyst toward the oxygen reduction reaction has been established. The proposed experimental procedure could serve as a general reference for determining the stability of electrocatalysts for different electrochemical systems.

Carbon nanotubes (CNTs), graphene aerogels (GAs), and their hybrid (CNT-GA) prepared by hydrothermal treatment were tested in the electrocatalytic oxygen reduction reaction (ORR). The importance of porous structure derived from the combination of mesoporosity coming from CNTs with macroporosity stemming from GAs was evidenced because the hybrid carbon material exhibited synergistic performance in terms of kinetic current and onset potential. Different electrocatalysts were prepared based on these hybrids doped with nitrogen using different precursors and also supporting Fe nanoparticles. N-doped carbon hybrids showed higher electrocatalytic activity than their undoped counterparts. Nevertheless, both doped and undoped materials provided a mixed two and four electron reduction. On the other hand, the addition of a Fe precursor and phenanthroline to the CNT-GA allowed preparing an N-doped hybrid containing Fe nanoparticles which favored the 4-electron oxygen reduction to water, thus being an excellent candidate as a structured cathode in fuel cells.

According to the Financial Times the steel industry emissions accounted for 7–9% of total greenhouse gases emissions worldwide in 2019. The main contribution to those emissions is directly related to the use of fossil coke and coal as fuels and reducing agents. Four solutions can be adopted to address such issue: direct reduction with hydrogen or syngas, electric arc furnaces, carbon capture and storage and use of biofuels (for example the so called “biocarbon”). These solutions can be also integrated. We propose applying innovative methods to produce biocarbon by pelletizing charcoal with pyrolysis oils and reheating it at high temperatures, to obtain materials with sufficient hardness, reduced porosity and proper reactivity. Once upgraded biocarbon can comply with the requirements usually needed for metallurgical coke. We present in this paper the results of a technical and economic analysis plus an environmental analysis on the expected final use of biocarbon in the silicon and steel industry.

Dual metal FeCo has great potential as Pt-free catalyst in various applications, such as cathodic catalyst for fuel cells, in order to reduce the cost significantly and make fuel cell commercialization, viable. In this study, dual metal FeCo catalyst supported on carbon Vulcan XC-72, carbon nanotubes (CNT), and reduced graphene oxide (rGO) were successfully prepared via facile co-precipitation method with varying weight ratios of Fe and Co. The structure of the as-prepared catalysts was characterized by powder X-ray diffraction (XRD), scanning electron micrographs (SEM), and X-ray photoelectron spectroscopy (XPS). The XPS analysis revealed that CoFe2O4 were present on the catalyst particle surface with different Fe to Co ratio. The emergence of the new peak at 530.5 eV is assigned to the deposition of CoFe2O4, which is enabled via Fe-O-Co bonds. The FeCo/rGO catalyst with weight ratio of 2:1 exhibited the optimum performance for oxygen reduction reaction (ORR), with reduction peak of 0.163 mA cm(-2) at 0.385 V vs. Ag/AgCl in an acidic media. The experimental result suggested that the dual metal FeCo catalyst display favourable electrocatalytic activity towards ORR and appears to be a promising cathodic electrocatalyst for an acidic fuel cell.

Pt-supported on multi-walled carbon nanotubes (MWCNT) and N-modified MWCNT (N-MWCNT) catalysts are synthesized by pyrolysis from emeraldine solution and microemulsion. Their electrochemical properties and carbon corrosion resistance in a Proton Exchange Membrane Fuel Cell (PEMFC) are compared with a commercial Pt/Vulcan catalyst through I–V curves, cyclic voltammetry and CO stripping. The initial fuel cell performances of the Pt/(N-)MWCNT catalysts are superior to Pt/Vulcan. The corrosion of the catalysts is quantified by the continuous measure of the CO2 release by online-mass spectrometry during potentiodynamic cycling between 0.1 and 1.6 V at 80 °C. The results show that Pt/MWCNT (with the lowest double-layer capacity) is the most stable catalyst followed by Pt/N-MWCNT and Pt/Vulcan, initially losing carbon at a rate of 1.1, 3.4 and 4.7 μgC (mg Ctot)−1 cycle−1, respectively. After about 30% carbon loss (50–70 cycles) all catalysts corrode at an approximate rate of 5.5 μgC mg−1 cycle−1. At this stage, all show similar electrochemical surface area and double-layer capacity. However, the substantial diminution of the initially very thick and porous Pt/(N-)MWCNT catalyst layers after corrosion consequences in lower fuel cell performance compared to the structurally less affected Pt/Vulcan electrode. The results clearly reveal that CNT-based catalyst supports are more corrosion resistant compared to state-of-the-art Vulcan. Moreover, the performance of the corroded electrodes envisages the importance of electrode porosity., QC 20200304

Zeolitic-imidazolate-frameworks-8 (ZIF-8) derivatives have recently been demonstrated as one of the most ideal precursors to prepare single-atom metal catalysts for oxygen reduction reaction (ORR). However, abundant single-atom metal sites are buried in the derived carbon nanoparticles, rendering them useless for ORR. Here a novel ZIF-8 “thermal melting” strategy is proposed to prepare a high specific surface area of Fe-N-doped graphene nanosheets (Fe-N/GNs) with single-atom Fe-sites on the surface which are accessible to electrolytes, optimizing their utilization and improving ORR activity. As a result, the Fe-N/GNs material exhibits excellent ORR activity with half-wave potentials of 0.903 V in alkaline media and 0.837 V in acidic media, which are comparable to commercial Pt/C catalysts. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The corrosion of the transport tank materials made of stainless steel 316Ti is investigated in a solution containing 12-15% of the commercial sodium hypochlorite solution. Using the electrochemical techniques, weight loss measurements, and optical microscope, it is shown that corrosion occurs due to the metastable pitting. It is proposed that formed metal oxides corrosion product could catalyzed chemical decomposition of hypochlorite solution to oxygen, which provokes the positive shift of the corrosion potentials into the region of metastable pitting.

Metal porphyrins have received sustained attention due to their remarkable catalytic properties. However, the catalytic activities of porphyrins are still moderate for oxygen reduction /evolution (ORR/OER) due to the high binding energies between the catalyst and reactant. Herein, we propose a novel strategy to modulate the binding energies of the oxygenated intermediates by introducing electron coupling between the substrate and the metal porphyrin. Our results reveal remarkable enhancement of OER/ORR performance when the Co-porphyrin molecule is supported on the graphene/Ni (111) substrate. The ORR/OER overpotentials can be greatly reduced, in particular for ORR from 0.6 V to 0.31 V. The enhanced ORR/OER activity of Co-porphyrin/graphene/Ni system stems from the electronic coupling between the catalyst and the substrate that modulates the binding strength between catalytic active sites and the reaction intermediates. Our study represents an efficient strategy to design low-cost, high performance, bifunctional electrocatalysts for the application in rechargeable metal-air batteries.

Single-atom catalysts (SACs) have attracted much attentions due to the advantages of high catalysis efficiency and selectivity. However, the controllable and efficient synthesis of SACs remains a significant challenge. Herein, we report a controlled one-pot synthesis of nickel single atoms embedded on nitrogen-doped carbon nanotubes (NiSA−N−CNT) and nitrogen-doped graphene (NiSA−N−G). The formation of NiSA−N−CNT is due to the solid-to-solid rolling up mechanism during the high temperature pyrolysis at 800 °C from the stacked and layered Ni-doped g-C3N4, g-C3N4−Ni structure to a tubular CNT structure. Addition of citric acid introduces an amorphous carbon source on the layered g-C3N4−Ni and after annealing at the same temperature of 800 °C, instead of formation of NiSA−N−CNT, Ni single atoms embedded in planar graphene type supports, NiSA−N−G were obtained. The density functional theory (DFT) calculation indicates the introduction of amorphous carbon source substantially reduces the structure fluctuation or curvature of layered g-C3N4-Ni intermediate products, thus interrupting the solid-to-solid rolling process and leading to the formation of planar graphene type supports for Ni single atoms. The as-synthesized NiSA−N−G with Ni atomic loading of ∼6 wt% catalysts shows a better activity and stability for the CO2 reduction reaction (CO2RR) than NiSA−N−CNT with Ni atomic loading of ∼15 wt% due to the open and exposed Ni single atom active sites in NiSA−N−G. This study demonstrates for the first time the feasibility in the control of the microstructure of carbon supports in the synthesis of SACs.

Photoelectrochemical (PEC) water splitting is an attractive strategy for the large-scale production of renewable hydrogen from water. Developing cost-effective, active and stable semiconducting photoelectrodes is extremely important for achieving PEC water splitting with high solar-to-hydrogen efficiency. Perovskite oxides as a large family of semiconducting metal oxides are extensively investigated as electrodes in PEC water splitting owing to their abundance, high (photo)electrochemical stability, compositional and structural flexibility allowing the achievement of high electrocatalytic activity, superior sunlight absorption capability and precise control and tuning of band gaps and band edges. In this review, the research progress in the design, development, and application of perovskite oxides in PEC water splitting is summarized, with a special emphasis placed on understanding the relationship between the composition/structure and (photo)electrochemical activity.

Chemical synthesis of platinum-rare earth metal (Pt-RE) nanoalloys, one of the most active catalysts for the oxygen re-duction reaction, has been a formidable challenge, mainly due to the vastly different standard reduction potentials of the two metals and high oxophilicity of the latter. Here we report a universal chemical process to prepare Pt-RE nanoalloys with tunable compositions and particle sizes. Pt and RE metal ions from the most common hydrated metal salts are first atomically embedded into an in-situ formed C-N network, yielding a stable compound insensitive to O2 and H2O. The Pt-RE nanoalloys are subsequently obtained by heating the compound under a mild reducing atmosphere (e.g. 3.3% H2/Ar). The key intermediate step of the process is the formation of RE carbodiimides (RE2(CN2)3) along with Pt particles. This synthesis mechanism suggests an efficient strategy to prepare nanoalloys with highly reactive metals.

The development of active and low-cost electrocatalysts for the oxygen reduction reaction (ORR) is crucial for the sustainable commercialization of fuel cell technologies. In this study, we have synthetized Me/Mo2C (Me = Fe, Co, Cu)-based composites embedded in N- and P-dual doped carbon by means of inexpensive industrial materials, such as melamine and chitosan, as C and N sources, and the heteropolyacid H3PMo12O40 as P and Mo precursor. The effect of the transition metal (Fe, Co, and Cu) on the ORR in alkaline medium has been investigated. The physicochemical properties of the electrocatalysts were performed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM). Activity towards ORR was carried out in a three-electrode cell using a ring-disk electrode in 0.1M NaOH. The results obtained clearly show the important role played by each transition metal (Fe, Co, and Cu) in the electrochemical activity. Among them, Fe gives rise to the best performing composite in carrying out the oxygen reduction reaction. The formation Fe3C/Mo2C species embedded in N- and P-dual doped carbon seems to be the determining role in the increase of the ORR performance.

Carbon plays a significant role in the development of electrode materials used in, for example, catalysis, energy storage and sensing. Graphene-based coatings and carbon nanotubes have expanded that role through nanostructuring of hybrids or the formation of composites. In particular, the formation of hybrids of nanocarbons with iridium oxide yield nanostructured materials through direct anodic deposition, which have substantially improved charge capacities vs. pure IrOx. Modification of the possible redox sites, new structuring of the hybrids and increased charge capacities are expected as a result. This work shows that nitrogen (N)-doped graphenes, as part of an IrOx hybrid, offer a new redox chemistry on graphene oxide through electrochemical modulation of the redox states of nitrogen in graphene, and yield stable nitro groups bound to carbon, which have, so far, the largest oxidation state reported in N-doped graphene. The hybrid materials are obtained in the form of coatings thanks to spontaneous adhesion of iridium oxo species on N-doped graphenes and further anodic electrodeposition of the mixture. While the oxidizing synthesis process already involves modification of the oxidation state of nitrogen, further electrochemical cycling evidences the electrochemical processes for both the IrOx and N groups attached to the graphene oxide. All the hybrids obtained present a wide range of nitrogen-based groups that include the nitro group, and a significant charge capacity that remains large upon electrochemical cycling and that involves all the faradaic processes from the iridium and graphene components. One hybrid, in particular, which includes the highest starting oxidation state, reaches a significantly higher charge capacity, higher even than the graphene oxide hybrid, and with 70% retention upon cycling. Although nitrogen doping of graphene is considered to be a reducing process, this study shows that an oxidizing range of nitrogen doping is also possible. IrOx

© 2019 Elsevier B.V. From a safety perspective, it is vital to have fast responding gas sensors for toxic and explosive gases in the event of a gas leak. Amperometric gas sensors have been developed for such a purpose, but their response times are often relatively slow – on the order of 50 seconds or more. In this work, we have developed sensors for hydrogen gas that demonstrate ultra-fast response times. The sensor consists of an array of gold microchannel electrodes, electrodeposited with platinum nanoparticles (PtNPs)to enable hydrogen electroactivity. Very thin layers (∼9 μm)of room temperature ionic liquids (RTILs)result in an extremely fast response time of only 2 s, significantly faster than the other conventional electrodes examined (unmodified Pt electrode, and PtNP modified Au electrode). The RTIL layer in the microchannels is much thinner than the channel length, showing an interesting yet complex diffusion pattern and characteristic thin-layer behavior. At short times (e.g. on the timescale of cyclic voltammetry), the oxidation current is smaller and steady-state in nature, compared to macrodisk electrodes. At longer times (e.g. using long-term chronoamperometry), the diffusion layer is large for all surfaces and extends to the liquid/gas phase boundary, where the gas is continuously replenished from the flowing gas stream. Thus, the current response is the largest on the microchannel electrode, resulting in the highest sensitivity and lowest limit of detection for hydrogen. These microchannel electrodes appear to be highly promising surfaces for the ultrafast detection of hydrogen gas, particularly at relevant concentrations close to, or below, the lower explosive limit of 4 vol-% H2.

The development of efficient Fe-N-C materials enriched with single-atom Fe sites toward the oxygen reduction reaction (ORR) is still a great challenge because Fe atoms are mobile and easily aggregate into nanoparticles during the higherature treatment. Herein, we proposed a facile and universal secondary-atom-assisted strategy to prepare atomic iron sites with high density hosted on porous nitrogen-doped carbon nanowires (Fe-NCNWs). The Fe-NCNWs showed an impressive half-wave potential (E1/2) of 0.91 V and average kinetic current density (JK) of 6.0 mA cm-2 at 0.9 V in alkaline media. They also held a high ORR activity in acidic solution with the E1/2 of 0.82 V and average JK of 8.0 mA cm-2 at 0.8 V. Density functional theory calculations demonstrated that the high ORR activity achieved is originated from single-atom iron sites that decrease the energy barrier in the reaction path efficiently. © 2019 American Chemical Society.

The use of dispersive single-atom metals anchored on functionalized carbon nanomaterials as electrocatalysts for electrochemical energy conversion reactions represents a burgeoning area of research, due to their unique characteristics of low coordination number, uniform coordination environment, and maximum atomic utilization. Here we highlight the advanced synthetic methods, characterization techniques, and electrochemical applications for carbon-based single-atom metal catalysts, and provide illustrative correlations between molecular/electronic structures and specific catalytic activity for O2 reduction, water splitting, and other emerging reactions including CO2 reduction, H2O2 production, and N2 reduction. We also discuss fundamental principles for the future design of carbon-based single-atom metal catalysts for specific electrochemical reactions. In addition, we explore the challenges and opportunities that lie ahead in further work with carbon-based single-atom metal electrocatalysts. © 2019, Springer Nature Switzerland AG.

The effect of direct current (DC) electric field and electrolyte layer thickness on oxygen reduction in simulated atmospheric environment were investigated using electrochemical measurements. The results show that the limiting diffusion current density (ilim) decreases with increasing the thin electrolyte layers (TELs) thickness but it increases with increasing the DC electric field intensity. The potential shifts negatively with the DC electric field. It is found that the DC electric field enables OH− ions to quickly migrate from the solution/electrode interface to the electrolyte layer. All these features promote the cathodic reduction process thereby enhancing the metal corrosion rate.

Nitrogen-doped graphitic materials as promising catalysts for the oxygen reduction reaction in fuel-cells have been mainly investigated under the graphitic versus pyridinic nitrogen-dopant dichotomy approach. However, we show here that the active sites, reaction mechanism, selectivity and even the origin of each behavior can be better understood when the stability of the possible active site and the eventual contribution of charge from the surface are considered separately. The roles in the reaction played by specific nitrogen-dopants, the hydrogenation of pyridinic nitrogen-dopants and the solvation effect are all clarified. The investigated activity is much more closely linked to the edges, where certain carbon atoms are sufficiently unstable or can be destabilized by means of adjacent nitrogen-dopants, and where reaction intermediates can be better relaxed, than to the presence of specific nitrogen-dopants. Unfortunately, high overpotentials and the undesired production of hydrogen peroxide appear to be unavoidable in the oxygen reduction to water on these materials.

In this work, a detailed kinetic analysis of the oxygen reduction reaction (ORR) on platinum is performed by applying steady and non-steady-state methodologies at stationary and rotating disk electrodes and by comparing experimental results to calculated curves via digital simulations. Results reveal the existence of a complex chemical–electrochemical–chemical–electrochemical initial reaction sequence, a CECE-mechanism, and the possible contribution of a parallel disproportionation process in acid media during the reaction. Under convection-controlled circumstances, the first charge-transfer step would be the rate-determining step (RDS) on bulk electrodes, in agreement with early reports, but at different working conditions other initial steps can become the RDS. Additionally, contrary to the current accepted view, results support the formation of a soluble intermediate in the initial, and fast, chemical reaction, with a short lifetime, compatible with the formation of either the hydroperoxyl radical, HO2*, or superoxide anion, O2–, followed by a fast protonation. In light of present results, possible mechanisms, including the oxidation of H2O2 that could be produced either by disproportionation or by reduction of HO2*, and/or O2–, radicals, are discussed. This interrelated reaction scheme would be the principal cause of large ORR overpotentials, but at the same time, it would open the opportunity for designing alternative catalysts beyond fundamental limits imposed by the apparent scaling relations between reaction intermediates, such as OHads, Oads, and HO2,ads adsorbates.