Probing Changes in the Local Structure of Active Bimetallic Mn/Ru Oxides during Oxygen Evolution.

Identifying the active site of catalysts for the oxygen evolution reaction (OER) is critical for the design of electrode materials that will outperform the current, expensive state-of-the-art catalyst, RuO2. Previous work shows that mixed Mn/Ru oxides show comparable performances in the OER, while reducing reliance on this expensive and scarce Pt-group metal. Herein, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy (XAS) are performed on mixed Mn/Ru oxide materials for the OER to understand structural and chemical changes at both metal sites during oxygen evolution. The results show that the Mn-content affects both the oxidation state and local coordination environment of Ru sites. Operando XAS experiments suggest that the presence of MnOx might be essential to achieve high activity likely by facilitating changes in the O-coordination sphere of Ru centers.

Demonstrating the source of inherent instability in NiFe LDH-based OER electrocatalysts.

Nickel-iron layered double hydroxides are known to be one of the most highly active catalysts for the oxygen evolution reaction in alkaline conditions. The high electrocatalytic activity of the material however cannot be sustained within the active voltage window on timescales consistent with commercial requirements. The goal of this work is to identify and prove the source of inherent catalyst instability by tracking changes in the material during OER activity. By combining in situ and ex situ Raman analyses we elucidate long-term effects on the catalyst performance from a changing crystallographic phase. In particular, we attribute electrochemically stimulated compositional degradation at active sites as the principal cause of the sharp loss of activity from NiFe LDHs shortly after the alkaline cell is turned on. EDX, XPS, and EELS analyses performed after OER also reveal noticeable leaching of Fe metals compared to Ni, principally from highly active edge sites. In addition, post-cycle analysis identified a ferrihydrite by-product formed from the leached Fe. Density functional theory calculations shed light on the thermodynamic driving force for the leaching of Fe metals and propose a dissolution pathway which involves [FeO4]2- removal at relevant OER potentials.

Low-temperature synthesis and electrocatalytic application of large-area PtTe2 thin films.

The synthesis of transition metal dichalcogenides (TMDs) has been a primary focus for 2D nanomaterial research over the last 10 years, however, only a small fraction of this research has been concentrated on transition metal ditellurides. In particular, nanoscale platinum ditelluride (PtTe2) has rarely been investigated, despite its potential applications in catalysis, photonics and spintronics. Of the reports published, the majority examine mechanically-exfoliated flakes from chemical vapor transport (CVT) grown crystals. This method produces high quality-crystals, ideal for fundamental studies. However, it is very resource intensive and difficult to scale up meaning there are significant obstacles to implementation in large-scale applications. In this report, the synthesis of thin films of PtTe2 through the reaction of solid-phase precursor films is described. This offers a production method for large-area, thickness-controlled PtTe2, potentially suitable for a number of applications. These polycrystalline PtTe2 films were grown at temperatures as low as 450 °C, significantly below the typical temperatures used in the CVT synthesis methods. Adjusting the growth parameters allowed the surface coverage and morphology of the films to be controlled. Analysis with scanning electron- and scanning tunneling microscopy indicated grain sizes of above 1 µm could be achieved, comparing favorably with typical values of ∼50 nm for polycrystalline films. To investigate their potential applicability, these films were examined as electrocatalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). The films showed promising catalytic behavior, however, the PtTe2 was found to undergo chemical transformation to a substoichiometric chalcogenide compound under ORR conditions. This study shows while PtTe2 is stable and highly useful for in HER, this property does not apply to ORR, which undergoes a fundamentally different mechanism. This study broadens our knowledge on the electrocatalysis of TMDs.

3D Printing for Electrochemical Energy Applications.

Additive manufacturing (also known as three-dimensional (3D) printing) is being extensively utilized in many areas of electrochemistry to produce electrodes and devices, as this technique allows for fast prototyping and is relatively low cost. Furthermore, there is a variety of 3D-printing technologies available, which include fused deposition modeling (FDM), inkjet printing, select laser melting (SLM), and stereolithography (SLA), making additive manufacturing a highly desirable technique for electrochemical purposes. In particular, over the last number of years, a significant amount of research into using 3D printing to create electrodes/devices for electrochemical energy conversion and storage has emerged. Strides have been made in this area; however, there are still a number of challenges and drawbacks that need to be overcome in order to 3D print active and stable electrodes/devices for electrochemical energy conversion and storage to rival that of the state-of-the-art. In this Review, we will give an overview of the reasoning behind using 3D printing for these electrochemical applications. We will then discuss how the electrochemical performance of the electrodes/devices are affected by the various 3D-printing technologies and by manipulating the 3D-printed electrodes by post modification techniques. Finally, we will give our insights into the future perspectives of this exciting field based on our discussion through this Review.

Visible-Light-Driven Single-Component BiVO4 Micromotors with the Autonomous Ability for Capturing Microorganisms.

Light-driven micro/nanomotors represent the next generation of automotive devices that can be easily actuated and controlled by using an external light source. As the field evolves, there is a need for developing more sophisticated micromachines that can fulfill diverse tasks in complex environments. Herein, we introduce single-component BiVO4 micromotors with well-defined micro/nanostructures that can swim both individually and as collectively assembled entities under visible-light irradiation. These devices can perform cargo loading and transport of passive particles as well as living microorganisms without any surface functionalization. Interestingly, after photoactivation, the BiVO4 micromotors exhibited an ability to seek and adhere to yeast cell walls, with the possibility to control their attachment/release by switching the light on/off, respectively. Taking advantage of the selective motor/fungal cells attachment, the fungicidal activity of BiVO4 micromotors under visible illumination was also demonstrated. The presented star-shaped BiVO4 micromotors, obtained by a hydrothermal synthesis, contribute to the potential large-scale fabrication of light-powered micromotors. Moreover, these multifunctional single-component micromachines with controlled self-propulsion, collective behavior, cargo transportation, and photocatalytic activity capabilities hold promising applications in sensing, biohybrids assembly, cargo delivery, and microbiological water pollution remediation.

Impurities in graphene/PLA 3D-printing filaments dramatically influence the electrochemical properties of the devices.

Herein, for the first time, we report on the presence of metal impurities in a widely reported and commercially available graphene/polylactic acid (PLA) 3D-printing filament and discuss the influence of these impurities on the electrochemical properties of as-printed and modified electrodes with said filament. Our findings show that the graphene component of this commercial filament contains Fe, Ti and Al impurities.

3D Printed Graphene Electrodes' Electrochemical Activation.

Three-dimensional (3D) printing technologies are emerging as an important tool for the manufacturing of electrodes for various electrochemistry applications. It has been previously shown that metal 3D electrodes, modified with metal oxides, are excellent catalysts for various electrochemical energy and sensing applications. However, the metal 3D printing process, also known as selective laser melting, is extremely costly. One alternative to metal-based electrodes for the aforementioned electrochemical applications is graphene-based electrodes. Nowadays, the printing of polymer-/graphene-based electrodes can be carried out in a matter of minutes using cheap and readily available 3D printers. Unfortunately, these polymer/graphene electrodes exhibit poor electrochemical activity in their native state. Herein, we report on a simple activation method for graphene/polymer 3D printed electrodes by a combined solvent and electrochemical route. The activated electrodes exhibit a dramatic increase in electrochemical activity with respect to the [Fe(CN)6]4-/3- redox couple and the hydrogen evolution reaction. Such in situ activation can be applied on-demand, thus providing a platform for the further widespread utilization of 3D printed graphene/polymer electrodes for electrochemistry.

Low-temperature synthesis and investigation into the formation mechanism of high quality Ni-Fe layered double hydroxides hexagonal platelets.

This paper describes the wet-chemistry synthesis of highly crystalline hexagonal flakes of Ni-Fe layered double hydroxide (LDH) produced at temperature as low as 100 °C. The flakes with diameter in the range of 0.5-1.5 µm and the thickness between 15 and 20 nm were obtained by homogeneous precipitation method with the use of triethanolamine (TEA) and urea. By analyzing the intermediate products, it is suggested that, differently from previous reports, a thermodynamically metastable iron oxyhydroxide and Ni-TEA complex are firstly formed at room temperature. Subsequently, when the mixture is heated to 100 °C and the pH increases due to the thermal decomposition of urea, Ni2+ and Fe3+ are slowly released and then recombine, thus leading to formation of pure, highly-crystalline Ni-Fe LDH flakes. This material showed promising results as an electrocatalyst in oxygen evolution reaction (OER) providing an overpotential value of 0.36 V.