Hybrid mesoporous electrodes evidence CISS effect on water oxidation.

Controlling product selectivity is essential for improving the efficiency of multi-product reactions. Electrochemical water oxidation is a reaction of main importance in different applications, e.g., renewable energy schemes and environmental protection, where H2O2 and O2 are the two principal products. In this Communication, the product selectivity of electrochemical water oxidation was controlled by making use of the chiral induced spin selectivity (CISS) effect at mesoporous-TiO2 on the molecule-modified Au substrate. Our results show a decrease in H2O2 formation when using chiral hetero-helicene molecules adsorbed on the Au substrate. We propose a mechanism for this kinetic effect based on the onset of CISS-induced spin polarization on the Au-helicene chiral interface. We also present a new tunable substrate to investigate the CISS mechanism.

Direct instrumental identification of catalytically active surface sites.

The activity of heterogeneous catalysts-which are involved in some 80 per cent of processes in the chemical and energy industries-is determined by the electronic structure of specific surface sites that offer optimal binding of reaction intermediates. Directly identifying and monitoring these sites during a reaction should therefore provide insight that might aid the targeted development of heterogeneous catalysts and electrocatalysts (those that participate in electrochemical reactions) for practical applications. The invention of the scanning tunnelling microscope (STM) and the electrochemical STM promised to deliver such imaging capabilities, and both have indeed contributed greatly to our atomistic understanding of heterogeneous catalysis. But although the STM has been used to probe and initiate surface reactions, and has even enabled local measurements of reactivity in some systems, it is not generally thought to be suited to the direct identification of catalytically active surface sites under reaction conditions. Here we demonstrate, however, that common STMs can readily map the catalytic activity of surfaces with high spatial resolution: we show that by monitoring relative changes in the tunnelling current noise, active sites can be distinguished in an almost quantitative fashion according to their ability to catalyse the hydrogen-evolution reaction or the oxygen-reduction reaction. These data allow us to evaluate directly the importance and relative contribution to overall catalyst activity of different defects and sites at the boundaries between two materials. With its ability to deliver such information and its ready applicability to different systems, we anticipate that our method will aid the rational design of heterogeneous catalysts.

In Situ Monitoring of the Surface Evolution of a Silver Electrode from Polycrystalline to Well-Defined Structures.

Capturing the surface-structural dynamics of metal electrocatalysts under certain electrochemical environments is intriguingly desired for understanding the behavior of various metal-based electrocatalysts. However, in situ monitoring of the evolution of a polycrystalline metal surface at the interface of electrode-electrolyte solutions at negative/positive potentials with high-resolution scanning tunneling microscopy (STM) is seldom. Here, we use electrochemical STM (EC-STM) for in situ monitoring of the surface evolution process of a silver electrode in both an aqueous sodium hydroxide solution and an ionic liquid of 1-methyl-1-octylpyrrolidinium bis(trifluoromethylsulfonyl) amide driven by negative potentials. We found silver underwent a surface change from a polycrystalline structure to a well-defined surface arrangement in both electrolytes. In NaOH aqueous solution, the silver surface transferred in several minutes at a turning-point potential where hydrogen adsorbed and formed mainly (111) and (100) pits. Controversially, the surface evolution in the ionic liquid was much slower than that in the aqueous solution, and cation adsorption was observed in a wide potential range. The surface evolution of silver is proposed to be linked to the surface adsorbates as well as the formation of their complexes with undercoordinated silver atoms. The results also show that cathodic annealing of polycrystalline silver is a cheap, easy, and reliable way to obtain quasi-ordered crystal surfaces.

Unprecedented High Oxygen Evolution Activity of Electrocatalysts Derived from Surface-Mounted Metal-Organic Frameworks.

The oxygen evolution reaction (OER) is a key process for renewable energy storage. However, developing non-noble metal OER electrocatalysts with high activity, long durability and scalability remains a major challenge. Herein, high OER activity and stability in alkaline solution were discovered for mixed nickel/cobalt hydroxide electrocatalysts, which were derived in one-step procedure from oriented surface-mounted metal-organic framework (SURMOF) thin films that had been directly grown layer-by-layer on macro- and microelectrode substrates. The obtained mass activity of ∼2.5 mA·µg-1 at the defined overpotential of 300 mV is 1 order of magnitude higher than that of the benchmarked IrO2 electrocatalyst and at least 3.5 times higher than the mass activity of any state-of-the-art NiFe-, FeCoW-, or NiCo-based electrocatalysts reported in the literature. The excellent morphology of the SURMOF-derived ultrathin electrocatalyst coating led to a high exposure of the most active Ni- and Co-based sites.

Enhancement of electrocatalysis through magnetic field effects on mass transport.

Magnetic field effects on electrocatalysis have recently gained attention due to the substantial enhancement of the oxygen evolution reaction (OER) on ferromagnetic catalysts. When detecting an enhanced catalytic activity, the effect of magnetic fields on mass transport must be assessed. In this study, we employ a specifically designed magneto-electrochemical system and non-magnetic electrodes to quantify magnetic field effects. Our findings reveal a marginal enhancement in reactions with high reactant availability, such as the OER, whereas substantial boosts exceeding 50% are observed in diffusion limited reactions, exemplified by the oxygen reduction reaction (ORR). Direct visualization and quantification of the whirling motion of ions under a magnetic field underscore the importance of Lorentz forces acting on the electrolyte ions, and demonstrate that bubbles' movement is a secondary phenomenon. Our results advance the fundamental understanding of magnetic fields in electrocatalysis and unveil new prospects for developing more efficient and sustainable energy conversion technologies.

Alpha-Nickel Hydroxide Coating of Metallic Nickel for Enhanced Alkaline Hydrogen Evolution.

In this work, alkaline hydrogen evolution reaction (HER) processes of three typical nickel-based electrocatalysts [i. e., Ni, α-Ni(OH)2 , and ß-Ni(OH)2 ] were investigated to probe critical factors that determine the activity and durability. The HER activity trend was observed as Ni≫α-Ni(OH)2 >ß-Ni(OH)2 , likely attributed to a synergy between metallic Ni and Ni(OH)2 components on the Ni surface and fast water dissociation kinetics on the α-Ni(OH)2 surface. With the HER proceeding, the metallic Ni surface, however, gradually became α-Ni(OH)2 , and α-Ni(OH)2 surface ultimately transformed into ß-phase, leading to a dramatic activity decrease of Ni electrodes. Therefore, Ni electrodes were coated with α-Ni(OH)2 nanosheets to slow down the nickel hydroxylation and optimize the surface ratio of Ni(OH)2 to metallic Ni. This simple coating procedure enhanced both activity and durability of Ni electrocatalysts.

Enhancement of electrocatalytic oxygen evolution by chiral molecular functionalization of hybrid 2D electrodes.

A sustainable future requires highly efficient energy conversion and storage processes, where electrocatalysis plays a crucial role. The activity of an electrocatalyst is governed by the binding energy towards the reaction intermediates, while the scaling relationships prevent the improvement of a catalytic system over its volcano-plot limits. To overcome these limitations, unconventional methods that are not fully determined by the surface binding energy can be helpful. Here, we use organic chiral molecules, i.e., hetero-helicenes such as thiadiazole-[7]helicene and bis(thiadiazole)-[8]helicene, to boost the oxygen evolution reaction (OER) by up to ca. 130 % (at the potential of 1.65 V vs. RHE) at state-of-the-art 2D Ni- and NiFe-based catalysts via a spin-polarization mechanism. Our results show that chiral molecule-functionalization is able to increase the OER activity of catalysts beyond the volcano limits. A guideline for optimizing the catalytic activity via chiral molecular functionalization of hybrid 2D electrodes is given.

In Situ Quantification of the Local Electrocatalytic Activity via Electrochemical Scanning Tunneling Microscopy.

Identification of catalytically active sites at solid/liquid interfaces under reaction conditions is an essential task to improve the catalyst design for sustainable energy devices. Electrochemical scanning tunneling microscopy (EC-STM) combines the control of the surface reactions with imaging on a nanoscale. When performing EC-STM under reaction conditions, the recorded analytical signal shows higher fluctuations (noise) at active sites compared to non-active sites (noise-EC-STM or n-EC-STM). In the past, this approach has been proven as a valid tool to identify the location of active sites. In this work, the authors show that this method can be extended to obtain quantitative information of the local activity. For the platinum(111) surface under oxygen reduction reaction conditions, a linear relationship between the STM noise level and a measure of reactivity, the turn-over frequency is found. Since it is known that the most active sites for this system are located at concave sites, the method has been applied to quantify the activity at steps. The obtained activity enhancement factors appeared to be in good agreement with the literature. Thus, n-EC-STM is a powerful method not only to in situ identify the location of active sites but also to determine and compare local reactivity.

Revealing Active Sites for Hydrogen Evolution at Pt and Pd Atomic Layers on Au Surfaces.

Identification of the most active surface sites is one of the key tasks in the development of new electrocatalytic materials. This is in many cases both time and resource consuming due to methodological difficulties of in situ detection of centers of this kind. In this work, we use the recently developed approach based on the analysis of the tunneling current noise recorded by electrochemical scanning tunneling microscopy (n-ECSTM) to compare the nature of the most active hydrogen evolution catalytic sites in a system consisting of sub-monolayers of platinum on a Au substrate to the one of palladium on Au. Our n-ECSTM measurements performed under reaction conditions show that in striking contrast to Pd islands on gold, where the most active centers are located close to the boundary between Au and palladium atoms, all Pt ad-atoms contribute to the overall activity rather equally at pH 1. Methodological aspects related to the use of n-ECSTM in electrocatalytic research are also discussed.

Multistage Mechanism of Lithium Intercalation into Graphite Anodes in the Presence of the Solid Electrolyte Interface.

A so-called solid electrolyte interface (SEI) in a lithium-ion battery largely determines the performance of the whole system. However, it is one of the least understood objects in these types of batteries. SEIs are formed during the initial charge-discharge cycles, prevent the organic electrolytes from further decomposition, and at the same time govern lithium intercalation into the graphite anodes. In this work, we use electrochemical impedance spectroscopy and atomic force microscopy to investigate the properties of a SEI film and an electrified "graphite/SEI/electrolyte interface". We reveal a multistage mechanism of lithium intercalation and de-intercalation in the case of graphite anodes covered by SEI. On the basis of this mechanism, we propose a relatively simple model, which perfectly explains the impedance response of the "graphite/SEI/electrolyte" interface at different temperatures and states of charge. From the whole data obtained in this work, it is suggested that not only Li+ but also negatively charged species, such as anions from the electrolyte or functional groups of the SEI, likely interact with the surface of the graphite anode.

Multiple Potentials of Maximum Entropy for a Na2Co[Fe(CN)6] Battery Electrode Material: Does the Electrolyte Composition Control the Interface?

Development of efficient schemes of energy storage is crucial for finding a solution for the "generation versus consumption" problem. Aqueous Na-ion batteries have been already recognized as one of the promising candidates for large-scale energy-storage systems. Despite noticeable progress in this field, the actual intercalation mechanisms governing these battery cells are yet to be fully comprehended. In this manuscript, we examine the electrode/electrolyte interface formed between electrodeposited Na2Co[Fe(CN)6] films and aqueous solutions. The investigated systems exhibit up to three potentials of maximum entropy (PMEs). To the best of our knowledge, the existence of multiple PMEs in electrochemical systems has never been reported in the literature. These unexpected results are, however, in line with the theory explaining the correlation between the water structure at the interface and the ease of the interfacial mass and charge transfer. Additionally, the obtained PMEs appear to largely depend on the anions' properties, most probably on the hydration energy of these species. This reveals the impact of the electrolyte composition on the interfacial processes in Na-ion batteries.