Eliminating Flooding-related Issues in Electrochemical CO2-to-CO Converters: Two Lines of Defense.

By using silver (Ag) in nanostructured (nanowire, nanosphere, etc.) or thin-layer form as a catalyst for electrochemical CO2 reduction, very high CO-forming selectivity of almost 100% can be achieved. Supported by gas diffusion layers (GDLs),  the reactant CO2 in the gas phase can approach and potentially access active Ag sites, which allows current densities in the range of a few hundred mA cm-2 to be reached. Yet, the stability of gas diffusion electrode (GDE) based electrochemical CO2-to-CO converters is far from perfect, and the activity of GDE cathodes, especially when operated at high current densities, often significantly decays during electrolyses after no more than a few hours. The primary reason of stability losses in GDE-based CO2-to-CO electrolysers is flooding: that is, the excess wetting of the GDE that prevents CO2 from reaching Ag catalytic sites. In the past years, the authors of this paper at Empa and at the University of Bern, cooperating with other partners of the National Competence Center for Research (NCCR) on Catalysis, took different approaches to overcome flooding. While opinions differ with regard to where the first line of defense in protecting GDEs from flooding should lie, a comparison of the recent results of the two groups gives unique insight into the nature of processes occurring in GDE cathodes used for CO2 electrolysis.

3D Printed Platform for Impedimetric Sensing of Liquids and Microfluidic Channels.

Fused deposition modeling 3D printing (FDM-3DP) employing electrically conductive filaments has recently been recognized as an exceptionally attractive tool for the manufacture of sensing devices. However, capabilities of 3DP electrodes to measure electric properties of materials have not yet been explored. To bridge this gap, we employ bimaterial FDM-3DP combining electrically conductive and insulating filaments to build an integrated platform for sensing conductivity and permittivity of liquids by impedance measurements. The functionality of the device is demonstrated by measuring conductivity of aqueous potassium chloride solution and bottled water samples and permittivity of water, ethanol, and their mixtures. We further implement an original idea of applying impedance measurements to investigate dimensions of 3DP channels as base structures of microfluidic devices, complemented by their optical microscopic analysis. We demonstrate that FDM-3DP allows the manufacture of microchannels of width down to 80 µm.

Functionalized Silver Nanoparticles as Colorimetric and Fluorimetric Sensor for Environmentally Toxic Mercury Ions: An Overview.

Nanoscience is a multifaceted field which encompasses metal nanoparticles (MNPs) having novel and size-related optical properties significantly different from the bulk level as well as at the atomic level. Amongst noble MNPs, the silver nanoparticles (AgNPs) have unique properties for metal interaction. Presently, there have been expedite reports which are taken under the review in virtue of sensing the mercury ions in aqueous media. Mercury dissemination in various forms contaminates the ecosystem. Globally mercury is ranked as the most toxic element and an urgent threat to humans since it causes major health issues. Employing MNPs, especially AgNPs for the detection of mercury ions is the economic, handy and apt method in contrast to time-consuming methods that use expensive instrumentations. The review highlights a study of colorimetric and fluorimetric detection of the level of Hg (II) ions in aqueous media selectively with high sensitivity in different courses of conditions using AgNPs synthesized by various approaches. Graphical abstract.

Environmental Control of Single-Molecule Junction Evolution and Conductance: A Case Study of Expanded Pyridinium Wiring.

Environmental control of single-molecule junction evolution and conductance was demonstrated for expanded pyridinium molecules by scanning tunneling microscopy break junction method and interpreted by quantum transport calculations including solvent molecules explicitly. Fully extended and highly conducting molecular junctions prevail in water environment as opposed to short and less conducting junctions formed in non-solvating mesitylene. A theoretical approach correctly models single-molecule conductance values considering the experimental junction length. Most pronounced difference in the molecular junction formation and conductance was identified for a molecule with the highest stabilization energy on the gold substrate confirming the importance of molecule-electrode interactions. Presented concept of tuning conductance through molecule-electrode interactions in the solvent-driven junctions can be used in the development of new molecular electronic devices.

Selected ion flow tube mass spectrometry analyses of isobaric compounds methanol and hydrazine in humid air.

RATIONALE: The volatile compounds generated by the electrochemical reduction of atmospheric carbon dioxide and nitrogen include isobaric methanol (CH3 OH) and, potentially, hydrazine (N2 H4 ). To achieve quantification of hydrazine molecules by selected ion flow tube mass spectrometry (SIFT-MS), its reactions with H3 O+ , NO+ and O2 + reagent ions must be understood. METHODS: A SIFT study (using a SIFT-MS instrument) was carried out to obtain rate coefficients and product ions for the reactions of H3 O+ , NO+ and O2 + reagent ions with N2 H4 and CH3 OH molecules present in the humid headspace of their aqueous solutions. Using the kinetics data obtained, solution headspace concentrations were determined for both compounds as a function of their liquid-phase concentrations at 10, 20 and 35°C. RESULTS: Both compounds react with H3 O+ ions via rapid proton transfer to produce CH3 OH2 + and H5 N2 + ions with the common m/z value of 33. It is revealed that NO+ rapidly transfers charge to N2 H4 (rate coefficient k = 2.3 × 10-9 cm3 s-1 ) but only slowly associates with CH3 OH (k2eff = 7.1 × 10-11 cm3 s-1 ). Thus, selective analysis can be achieved using both H3 O+ and NO+ reagent ions. The headspace methanol vapour concentration was found to increase with increasing solution temperature, but that of hydrazine decreased with an associated increase of ammonia (NH3 ) as measured with O2 + reagent ions. CONCLUSIONS: The isobaric compounds methanol and hydrazine can be separately analysed in real time by SIFT-MS using H3 O+ and NO+ reagent ions, even when they co-occur in humid air. The evolution of hydrazine from aqueous solutions can be quantitatively monitored together with its decomposition at elevated temperatures.

The development of a fully integrated 3D printed electrochemical platform and its application to investigate the chemical reaction between carbon dioxide and hydrazine.

The combination of computer assisted design and 3D printing has recently enabled fast and inexpensive manufacture of customized 'reactionware' for broad range of electrochemical applications. In this work bi-material fused deposition modeling 3D printing is utilized to construct an integrated platform based on a polyamide electrochemical cell and electrodes manufactured from a polylactic acid-carbon nanotube conductive composite. The cell contains separated compartments for the reference and counter electrode and enables reactants to be introduced and inspected under oxygen-free conditions. The developed platform was employed in a study investigating the electrochemical oxidation of aqueous hydrazine coupled to its bulk reaction with carbon dioxide. The analysis of cyclic voltammograms obtained in reaction mixtures with systematically varied composition confirmed that the reaction between hydrazine and carbon dioxide follows 1/1 stoichiometry and the corresponding equilibrium constant amounts to (2.8 ± 0.6) × 103. Experimental characteristics were verified by results of numerical simulations based on the finite-element-method.

Importance of the Anchor Group Position (Para versus Meta) in Tetraphenylmethane Tripods: Synthesis and Self-Assembly Features.

The efficient synthesis of tripodal platforms based on tetraphenylmethane with three acetyl-protected thiol groups in either meta or para positions relative to the central sp(3) carbon for deposition on Au (111) surfaces is reported. These platforms are intended to provide a vertical arrangement of the substituent in position 4 of the perpendicular phenyl ring and an electronic coupling to the gold substrate. The self-assembly features of both derivatives are analyzed on Au (111) surfaces by low-temperature ultra-high-vacuum STM, high-resolution X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and reductive voltammetric desorption studies. These experiments indicated that the meta derivative forms a well-ordered monolayer, with most of the anchoring groups bound to the surface, whereas the para derivative forms a multilayer film with physically adsorbed adlayers on the chemisorbed para monolayer. Single-molecule conductance values for both tripodal platforms are obtained through an STM break junction experiment.

Charge transport in C60-based dumbbell-type molecules: mechanically induced switching between two distinct conductance states.

Single molecule charge transport characteristics of buckminsterfullerene-capped symmetric fluorene-based dumbbell-type compound 1 were investigated by scanning tunneling microscopy break junction (STM-BJ), current sensing atomic force microscopy break junction (CS-AFM-BJ), and mechanically controlled break junction (MCBJ) techniques, under ambient conditions. We also show that compound 1 is able to form highly organized defect-free surface adlayers, allowing the molecules on the surface to be addressed specifically. Two distinct single molecule conductance states (called high G(H)(1) and low G(L)(1)) were observed, depending on the pressure exerted by the probe on the junction, thus allowing molecule 1 to function as a mechanically driven molecular switch. These two distinct conductance states were attributed to the electron tunneling through the buckminsterfullerene anchoring group and fully extended molecule 1, respectively. The assignment of conductance features to these configurations was further confirmed by control experiments with asymmetrically designed buckminsterfullerene derivative 2 as well as pristine buckminsterfullerene 3, both lacking the G(L) feature.

Pencil graphite electrodes for in-situ spectroelectrochemical sensing of reaction intermediates and products in organic solvents.

BACKGROUND: Spectroelectrochemistry (SEC) is a valuable analytical tool providing insights to reaction mechanisms and the structure of species involved in charge transfer reactions. Most of commercial SEC setups are based on platinum working electrodes where the adsorption of species involved in reactions often complicates their analysis. RESULTS: In this work, we employ an array of pencil graphite rods as an optically transparent working electrode in a custom-made air-tight thin-layer cell suitable for the SEC analysis performed here in acetonitrile as a representative non-aqueous solvent. The functionality of the device was demonstrated by UV-Vis SEC sensing of charge transfer reactions of ruthenium acetylacetonate, ferrocene and ethylviologen dibromide redox probes performed employing the cyclic voltammetry. The SEC response obtained for all three probes confirmed no adsorption and the absence of oxygen in the cell. Furthermore, we have developed and utilized finite element method numerical simulations considering charge transfer reactions coupled with the diffusional mass transport to model the cyclic voltammetric response and the reaction conversion in the thin-layer SEC cell. SIGNIFICANCE: Our work paves the way for easy-to-assemble customized air-tight adsorption-free SEC devices with the manufacturing costs well below those of commercially available platforms. Developed computational approaches have the predictive power for optimizing reaction conditions and the geometry of the SEC cell.

Charge transport in photoswitchable dimethyldihydropyrene-type single-molecule junctions.

The conductance properties of a photoswitchable dimethyldihydropyrene (DHP) derivative have been investigated for the first time in single-molecule junctions using the mechanically controllable break junction technique. We demonstrate that the reversible structure changes induced by isomerization of a single bispyridine-substituted DHP molecule are correlated with a large drop of the conductance value. We found a very high ON/OFF ratio (>10(4)) and an excellent reversibility of conductance switching.

Tetrathiafulvalene-oligo(para-phenyleneethynylene) conjugates: formation of multiple mixed-valence complexes upon electrochemical oxidation.

Short monodisperse oligo- (para-phenyleneethynylene) (pOPE) units bearing laterally attached tetrathio-substituted tetrathiofulvalene (TTF) units have been synthesised from functionalised aromatic building blocks by using the Sonogashira cross-coupling methodology. The unusual redox properties of these TTF-pOPE conjugates were observed by employing electrochemical methods, such as cyclic voltammetry and exhaustive electrolysis. We found that formally one half of the TTF units in the pOPE monomer 1, dimer 2, and trimer 3 (with 2, 4, and 6 TTF units, respectively) are electrochemically silent during the first-step oxidation at 0.49 V. We propose the formation of persistent mixed-valence complexes from the TTF and TTF(+·) units present in an equal ratio. Such mixed-valence dyads (single or multiple in the partially oxidised 1-3) exhibit an unusual stability towards oxidation until the potential of the second oxidation at 0.84 V is achieved. This finding suggests that below this potential the oxidation of the respective mix-valence complexes is extremely slow.

Batch fabrication of gold-gold nanogaps by E-beam lithography and electrochemical deposition.

We report on the successful development of a well-controlled two-step batch nano-fabrication process to achieve nanometer-size gaps at the wafer scale. The technique is based on an optimized electron-beam lithography process, which enables the fabrication of nanogaps in the range (15 ± 4) nm. Following this first step, the feedback-controlled electrochemical deposition of gold from an aqueous HAuCl4-based electrolyte is applied to further reduce the size of the gap down to about 0.3-1.0 nm. This protocol was successfully demonstrated by fabricating more than 385 nanogaps on a 4 inch wafer. The reproducible fabrication of nanogaps in the range between 0.3 and 1.0 nm opens up new perspectives for addressing the electrical and reactivity properties of single molecules and clusters in confined space under well-controlled conditions.

Electrochemical current-sensing atomic force microscopy in conductive solutions.

Insulated atomic force microscopy probes carrying gold conductive tips were fabricated and employed as bifunctional force and current sensors in electrolyte solutions under electrochemical potential control. The application of the probes for current-sensing imaging, force and current-distance spectroscopy as well as scanning electrochemical microscopy experiments was demonstrated.

Spectroelectrochemical sensing of reaction intermediates and products in an affordable fully 3D printed device.

Recent advances in fused deposition modelling 3D printing (FDM 3DP) and synthesis of printable electrically conductive materials enabled the manufacture of customized electrodes and electrochemical devices by this technique. The past couple of years have seen a boom in applying approaches of FDM 3DP in the realm of spectroelectrochemistry (SEC). Despite significant progress, reported designs of SEC devices still rely on conventionally manufactured optical components such as quartz windows and cuvettes. To bridge this technological gap, in this work we apply bi-material FDM 3DP combining electrically conductive and optically translucent filaments to manufacture working electrodes and cells, constituting a fully integrated microfluidic platform for transmission absorption UV-Vis SEC measurements. The cell design enables de-aeration of samples and their convenient handling and analysis. Employing cyclic voltammetric measurements with ruthenium(III) acetylacetonate, ethylviologen dibromide and ferrocenemethanol redox-active probes as model analytes, we demonstrate that the presented platform allows SEC sensing of reactants, intermediates and products of charge transfer reactions, including the inspection of their long-term stability. Approaches developed and presented in this work pave the way for manufacturing customized SEC devices with dramatically reduced costs compared to currently available commercial platforms.

Probing charge transfer through antifouling polymer brushes by electrochemical methods: The impact of supporting self-assembled monolayer chain length.

Ultrathin surface-tethered polymer brushes represent attractive platforms for a wide range of sensing applications in strategically vital areas such as medicine, forensics, or security. The recent trends in such developments towards "real world conditions" highlighted the role of zwitterionic poly(carboxybetaine) (pCB) brushes which provide excellent antifouling properties combined with bio-functionalization capacity. Highly dense pCB brushes are usually prepared by the "grafting from" polymerization triggered by initiators on self-assembled monolayers (SAMs). Here, multi-methodological experimental studies are pursued to elucidate the impact of the alkanethiolate SAM chain length (C6, C8 and C11) on structural and functional properties of antifouling poly(carboxybetaine methacrylamide) (pCBMAA) brush. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a custom-made 3D printed cell employing [Ru(NH3)6]3+/2+ redox probe were used to investigate penetrability of SAM/pCBMAA bilayers for small molecules and interfacial charge transfer characteristics. The biofouling resistance of pCBMAA brushes was characterized by surface plasmon resonance; ellipsometry and FT-IRRAS spectroscopy were used to determine swelling and relative density of the brushes synthesized from initiator-bearing SAMs with varied carbon chain length. The SAM length was found to have a substantial impact on all studied characteristics; the highest value of charge transfer resistance (Rct) was observed for denser pCBMAA on longer-chain (C11) SAM when compared to shorter (C8/C6) SAMs. The observed high value of Rct for C11 implies a limitation for the analytical performance of electrochemical sensing methods. At the same time, the pCBMAA brushes on C11 SAM exhibited the best bio-fouling resistance among inspected systems. This demonstrates that proper selection of supporting structures for brushes is critical in the design of these assemblies for biosensing applications.

Direct electrochemical determination of environmentally harmful pharmaceutical ciprofloxacin in 3D printed flow-through cell.

Rising amounts of antibiotic residues in wastewater cause serious problems including increased bacterial resistance. Wastewater treatment plants (WWTPs) do not, in the case of new, modern pharmaceuticals, ensure their complete removal. Ciprofloxacin (CIP) is one of many micropollutants that partially pass through WWTPs, implying that its monitoring is essential for the assessment of the water quality. In real sewage systems, the determination of CIP needs to be performed under flowing conditions, which calls for the deployment of inexpensive, robust, and easily integrable approaches such as electrochemical techniques. However, to the best of our knowledge, there is no report on the electrochemical determination of CIP in a flowing matrix. To bridge this gap, we perform here cyclic and square-wave voltammetric sensing study of CIP employing boron-doped diamond screen printed electrodes in a custom-made 3D printed flow-through cell to mimic conditions in real sewage systems. An irreversible two-step oxidation of CIP is demonstrated, with the first step providing clear Faradaic response as analytically relevant signal. This response was found to scale with the sample flow rate according to the prediction given by Levich equation. Our work provides an in-depth inspection of the electrochemical response of CIP under controlled-convection conditions, which is an essential prerequisite for monitoring this antibiotic in real flowing sewage systems.

Effective perspiration is essential to uphold the stability of zero-gap MEA-based cathodes used in CO2 electrolysers.

The application of gas diffusion electrodes (GDEs) for the electrochemical reduction of CO2 to value-added products creates the possibility of achieving current densities of a few hundred mA cm-2. To achieve stable operation at such high reaction rates remains, however, a challenging task, due to the flooding of the GDE. In order to mitigate flooding in a zero-gap membrane-electrode assembly (MEA) configuration, paths for effective electrolyte perspiration inside the GDE structure have to be kept open during the electrolysis process. Here we demonstrate that apart from the operational parameters of the electrolysis and the structural properties of the supporting gas diffusion layers, also the chemical composition of the applied catalyst inks can play a decisive role in the electrolyte management of GDEs used for CO2 electroreduction. In particular, the presence of excess amounts of polymeric capping agents (used to stabilize the catalyst nanoparticles) can lead to a blockage of micropores, which hinders perspiration and initiates the flooding of the microporous layer. Here we use a novel ICP-MS analysis-based approach to quantitatively monitor the amount of perspired electrolyte that exits a GDE-based CO2 electrolyser, and we show a direct correlation between the break-down of effective perspiration and the appearance of flooding-the latter ultimately leading to a loss of electrolyser stability. We recommend the use of an ultracentrifugation-based approach by which catalyst inks containing no excess amount of polymeric capping agents can be formulated. Using these inks, the stability of electrolyses can be ensured for much longer times.

Applicability of Selected 3D Printing Materials in Electrochemistry.

This manuscript investigates the chemical and structural stability of 3D printing materials (3DPMs) frequently used in electrochemistry. Four 3D printing materials were studied: Clear photopolymer, Elastic photopolymer, PET filament, and PLA filament. Their stability, solubility, structural changes, flexibility, hardness, and color changes were investigated after exposure to selected organic solvents and supporting electrolytes. Furthermore, the available potential windows and behavior of redox probes in selected supporting electrolytes were investigated before and after the exposure of the 3D-printed objects to the electrolytes at various working electrodes. Possible electrochemically active interferences with an origin from the 3DPMs were also monitored to provide a comprehensive outline for the use of 3DPMs in electrochemical platform manufacturing.

Cracks as Efficient Tools to Mitigate Flooding in Gas Diffusion Electrodes Used for the Electrochemical Reduction of Carbon Dioxide.

The advantage of employing gas diffusion electrodes (GDEs) in carbon dioxide reduction electrolyzers is that they allow CO2 to reach the catalyst in gaseous state, enabling current densities that are orders of magnitude larger than what is achievable in standard H-type cells. The gain in the reaction rate comes, however, at the cost of stability issues related to flooding that occurs when excess electrolyte permeates the micropores of the GDE, effectively blocking the access of CO2 to the catalyst. For electrolyzers operated with alkaline electrolytes, flooding leaves clear traces within the GDE in the form of precipitated potassium (hydrogen)carbonates. By analyzing the amount and distribution of precipitates, and by quantifying potassium salts transported through the GDE during operation (electrolyte perspiration), important information can be gained with regard to the extent and means of flooding. In this work, a novel combination of energy dispersive X-ray and inductively coupled plasma mass spectrometry based methods is employed to study flooding-related phenomena in GDEs differing in the abundance of cracks in the microporous layer. It is concluded that cracks play an important role in the electrolyte management of CO2 electrolyzers, and that electrolyte perspiration through cracks is paramount in avoiding flooding-related performance drops.

Nitrogen heteroaromatic cations by [2+2+2] cycloaddition.

A modular approach to the construction of monocationic quaternary N-heteroaromatic frameworks was developed capitalizing on a direct pyridine-type nitrogen quaternization followed by metal-catalyzed [2+2+2] cycloaddition with gaseous acetylene. The flexibility of the route is demonstrated on 12 diverse scaffolds based on pyridinium, quinolinium, thiazolium, benzothiazolium, imidazolium, and pyrimidinium. Electrochemical study revealed a quinolinium redox system with two electrochemically distinct forms that are interconverted by a homogeneous chemical reaction triggered by fast electron transfers (reduction at -0.7 V and oxidation at -0.05 V).