Allotrope-dependent activity-stability relationships of molybdenum sulfide hydrogen evolution electrocatalysts.

Molybdenum disulfide (MoS2) is widely regarded as a competitive hydrogen evolution reaction (HER) catalyst to replace platinum in proton exchange membrane water electrolysers (PEMWEs). Despite the extensive knowledge of its HER activity, stability insights under HER operation are scarce. This is paramount to ensure long-term operation of Pt-free PEMWEs, and gain full understanding on the electrocatalytically-induced processes responsible for HER active site generation. The latter are highly dependent on the MoS2 allotropic phase, and still under debate. We rigorously assess these by simultaneously monitoring Mo and S dissolution products using a dedicated scanning flow cell coupled with downstream analytics (ICP-MS), besides an electrochemical mass spectrometry setup for volatile species analysis. We observe that MoS2 stability is allotrope-dependent: lamellar-like MoS2 is highly unstable under open circuit conditions, whereas cluster-like amorphous MoS3-x instability is induced by a severe S loss during the HER and undercoordinated Mo site generation. Guidelines to operate non-noble PEMWEs are therefore provided based on the stability number metrics, and an HER mechanism which accounts for Mo and S dissolution pathways is proposed.

Edges of Layered FePSe3 Exhibit Increased Electrochemical and Electrocatalytic Activity Compared to Basal Planes.

Transition metal trichalcogenphosphites (MPX3), belonging to the class of 2D materials, are potentially viable electrocatalysts for the hydrogen evolution reaction (HER). Many 2D and layered materials exhibit different magnitudes of electrochemical and electrocatalytic activity at their edge and basal sites. To find out whether edges or basal planes are the primary sites for catalytic processes at these compounds, we studied the local electrochemical and electrocatalytic activity of FePSe3, an MPX3 representative that was previously found to be catalytically active. Using scanning electrochemical microscopy, we discovered that electrochemical processes and the HER are occurring at an increased rate at edge-like defects of FePSe3 crystals. We correlate our observations using optical microscopy, confocal laser scanning microscopy, scanning electron microscopy, and electron-dispersive X-ray spectroscopy. These findings have profound implications for the application of these materials for electrochemistry as well as for understanding general rules governing the electrochemical performance of layered compounds.

Multi-Wavelength Light-Responsive Metal-Phenolic Network-Based Microrobots for Reactive Species Scavenging.

Light-driven microrobots with different propulsion mechanisms have attracted great attention in microrobot synthesis and applications. However, current systems rely heavily on precious metals, using a complex synthesis process and limited working wavelength. It is therefore of great interest to fabricate microrobots that can be driven by multi-wavelength irradiation and with simple components. Here, metal-phenolic network (MPN)-based microrobots are synthesized using a sacrificial polystyrene bead template and an extra capping is added to regulate their symmetry. The hollow MPN microrobots with different layers of capping are capable of moving under both near-infrared (NIR) irradiation and ultraviolet (UV) irradiation, without fuel. The velocity of the microrobots under irradiation is altered by the thickness of the asymmetric capping and their motion could be manipulated remotely by switching the NIR or UV irradiation on and off. With light-driven mobility, the reactive oxygen and nitrogen species (RONS) scavenging activity of the microrobots is significantly increased. Therefore, this proposed microrobot system provides a synthesis strategy to develop asymmetric light-navigated microrobots for future medical treatment with tunable structure, multi-wavelength light-responsive mobility, and great RONS scavenging capacity.

Nickel Sulfide Microrockets as Self-Propelled Energy Storage Devices to Power Electronic Circuits "On-Demand".

Miniaturized energy storage devices are essential to power the growing number and variety of microelectronic technologies. Here, a concept of self-propelled microscale energy storage elements that can move, reach, and power electronic circuits is reported. Microrockets consisting of a nickel sulfide (NiS) outer layer and a Pt inner layer are prepared by template-assisted electrodeposition, and designed to store energy through NiS-mediated redox reactions and propel via the Pt-catalyzed decomposition of H2 O2 fuel. Scanning electrochemical microscopy allows visualizing and studying the energy storage ability of a single microrocket, revealing its pseudocapacitive nature. This proves the great potential of such technique in the field of micro/nanomotors. On-demand delivery of energy storage units to electronic circuits has been demonstrated by releasing microrockets on an interdigitated array electrode as an example of electronic circuit. Owing to their self-propulsion ability, they reach the active area of the electrode and, in principle, power its functions. These autonomously moving energy storage devices will be employed for next-generation electronics to store and deliver energy in previously inaccessible locations.

Catalyst Formation and In Operando Monitoring of the Electrocatalytic Activity in Flow Reactors.

Flow reactors are of increasing importance and have become crucial devices due to their wide application in chemical synthesis, electrochemical hydrogen evolution reaction (HER), or electrochemical waste water treatment. In many of these applications, catalyst materials such as transition-metal chalcogenides (TMCs) for the HER, provide the desired electrochemical reactivity for the HER. Generally, the flow electrolyzers' performance is evaluated as the overall output, but the decrease in activity of the electrolyzer is due to localized failure of the catalyst. Herein, we present a method for the spatially resolved (tens of micrometers) In Operando analysis of the catalytic activity under real operation conditions as well as the localized deposition of the catalyst in an operating model flow reactor. For these purposes, scanning electrochemical microscopy was applied for MoSx catalyst deposition and for localized tracking of the TMC activity with a resolution of 25 µm. This approach offers detailed information about the catalytic performance and should find broad application for the characterization and optimization of flow reactor catalysis under real operational conditions.

3D Printing Temperature Tailors Electrical and Electrochemical Properties through Changing Inner Distribution of Graphite/Polymer.

The rise of 3D printing technology, with fused deposition modeling as one of the simplest and most widely used techniques, has empowered an increasing interest for composite filaments, providing additional functionality to 3D-printed components. For future applications, like electrochemical energy storage, energy conversion, and sensing, the tuning of the electrochemical properties of the filament and its characterization is of eminent importance to improve the performance of 3D-printed devices. In this work, customized conductive graphite/poly(lactic acid) filament with a percentage of graphite filler close to the conductivity percolation limit is fabricated and 3D-printed into electrochemical devices. Detailed scanning electrochemical microscopy investigations demonstrate that 3D-printing temperature has a dramatic effect on the conductivity and electrochemical performance due to a changed conducive filler/polymer distribution. This may allow, e.g., 3D printing of active/inactive parts of the same structure from the same filament when changing the 3D printing nozzle temperature. These tailored properties can have profound influence on the application of these 3D-printed composites, which can lead to a dramatically different functionality of the final electrical, electrochemical, and energy storage device.

Local electrochemical activity of transition metal dichalcogenides and their heterojunctions on 3D-printed nanocarbon surfaces.

Transition metal dichalcogenides (TMDs) have shown to be promising catalysts for the electrochemical hydrogen evolution reaction (HER) and 3D-printing enables fast prototyping and manufacturing of water splitting devices. However, the merging of TMDs with complex 3D-printed surfaces and nanostructures as well as their localized characterization remains challenging. In this work, electrodeposition of MoS2 and WS2 and their heterojunctions are used to modify thermally activated 3D-printed nanocarbon structures. Their electrochemical performance for the HER is investigated macroscopically by linear sweep voltammetry and microscopically by scanning electrochemical microscopy. This study demonstrates different local HER active sites of MoS2 and WS2 within the 3D-printed nanocarbon structure that are not solely located at the outer surface, but also in the interior up to ∼150 µm for MoS2 and ∼300 µm for WS2.

Atomic Layer Deposition of Electrocatalytic Insulator Al2O3 on Three-Dimensional Printed Nanocarbons.

The advantages of three-dimensional (3D) printing technologies, such as rapid-prototyping and the freedom to customize electrodes in any design, have elevated the benchmark of conventional electrochemical studies. Furthermore, the 3D printed electrodes conveniently accommodate other active layers for diverse applications such as energy storage, catalysis, and sensors. Nevertheless, to enhance a complex 3D structure while preserving the fine morphology, conformal deposition by atomic layer deposition (ALD) technique is a powerful solution. Herein, we present the concept of coating Al2O3 by ALD with different thicknesses from 20 to 120 cycles on the 3D printed nanocarbon/PLA electrodes for the electrocatalytic oxidation of catechol as an important biomarker. Overall, 80 ALD cycle Al2O3 achieved an optimum thickness for catechol electrocatalysis. This is resonated with the enhanced adsorption of catechol at the electrode surface and efficient electron transfer, according to the two-proton, two-electron-transfer mechanism, as well as for the passivation of surface defects of the nanocarbon electrode. This work compellingly demonstrates the prospect of 3D printed electrodes modified by a functional layer utilizing a low-temperature ALD process that can be extended to other arbitrary surfaces.

Inherent Impurities in Graphene/Polylactic Acid Filament Strongly Influence on the Capacitive Performance of 3D-Printed Electrode.

Additive manufacturing or 3D-printing have become promising fabrication techniques in the field of electrochemical energy storage applications such as supercapacitors, and batteries. Of late, a commercially available graphene/polylactic acid (PLA) filament has been commonly used for Fused Deposition Modeling (FDM) 3D-printing in the fabrication of electrodes for supercapacitors and Li-ion batteries. This graphene/PLA filament contains metal-based impurities such as titanium oxide and iron oxide. In this study, we show a strong influence of inherent impurities in the graphene/PLA filament for supercapacitor applications. A 3D-printed electrode is prepared and subsequently thermally activated for electrochemical measurement. A deep insight has been taken to look into the pseudocapacitive contribution from the metal-based impurities which significantly enhanced the overall capacitance of the 3D-printed graphene/PLA electrode. A systematic approach has been shown to remove the impurities from the printed electrodes. This has a broad implication on the interpretation of the capacitance of 3D-printed composites.

Scanning Electrochemical Microscopy of Electrically Heated Wire Substrates.

We report a new configuration for enhancing the performance of scanning electrochemical microscopy (SECM) via heating of the substrate electrode. A flattened Pt microwire was employed as the substrate electrode. The substrate was heated by an alternating current (AC), resulting in an increased mass transfer between the wire surface and the bulk solution. The electrochemical response of the Pt wire during heating was investigated by means of cyclic voltammetry (CV). The open circuit potential (OCP) of the wire was recorded over time, while varied heating currents were applied to investigate the time needed for establishing steady-state conditions. Diffusion layer studies were carried out by performing probe approach curves (PACs) for various measuring modes of SECM. Finally, imaging studies of a heated substrate electrode surface, applying feedback, substrate generation/tip collection (SG/TC), and the competition mode of SECM, were performed and compared with room temperature results.

Scanning Electrochemical Microscopy with Forced Convection Introduced by High-Precision Stirring.

In the present report the well-known advantages of hydrodynamic mass transport in electrochemical systems are used in combination with scanning electrochemical microscopy (SECM). The hydrodynamic SECM system integrates a high-precision stirring device into the experimental setup. The well-defined stirring of the SECM electrolyte results in steady state diffusion layer characteristics in the vicinity of large substrate electrodes operated in chronoamperometric measuring mode. For a range of rotation frequencies of a rotating cylinder the thickness and the stability of the diffusion layer was studied by hydrodynamic SECM in the substrate generation/tip collection (SG/TC) as well as in the competition mode using ferrocene methanol as redox mediator. Different UME probe dimensions ranging from Pt diameters of 20 µm down to 0.6 µm were used. The smallest probe with dPt = 0.6 µm was found most suitable for these studies due to the almost convection-independent amperometric response associated with subµm electrodes. Additionally, preliminary studies of hydrodynamic SECM imaging of a 2 mm Pt disk electrode surface in the SG/TC mode based on in situ produced hydrogen as a mediator are presented. Comparative images measured in the conventional positive feedback mode in quiescent solution show that hydrodynamic SECM offers attractive complementary information.