Chronoamperometric Measurements Research Articles

Microfluidic flow sensor based on chronoamperometric measurements in a microchannel

Microfluidics explores the fluid behavior at micron scale and is therefore suited to applications that need precise manipulation of fluids at small length or volume scales. In a span of over two decades, microfluidics has become an essential tool for modern genome sequencing platforms, single-cell analysis and common diagnostic tests. Despite many successful applications, the field has various challenges: Fabrication processes are yet to transition to commercial materials, microfluidic systems are reliant on skilled operators, and supporting equipment. Technological innovations in automation are needed to enable easy to use, completely on-chip microfluidic systems. Sensors are a critical component of any automated system. Fluid and flow properties such as flow rate, pressure, temperature, viscosity are critical to applications in drug development, and material/chemical synthesis. The flow rate (μL/min or nL/min) predictions based on external (off-chip) flow measurements can lead to erroneous calculations. The present work explores a technique based on chronoamperometry to measure flow rates inside a microchannel. Chronoamperometry based redox cycling of aqueous NaCl was performed by using interdigitated electrodes (IDE). The sensor measures current transients (which are modulated by the flow rate of the solution) effected by redox reactions on surface of the electrodes. The sensor demonstrated a sensitivity of 0.016 (μL/min)−1 change in charge transfer per unit change in flow rate and 3σ resolution of 9.3 μL/min. The calibration curve is linear in the range 0 – 200 μL/min, with a limit of detection (LoD) of 5 μL/min, making it suitable for various microfluidics applications.

Two-step synthesis of tungsten disulfide and its evaluation as electrocatalyst for hydrogen evolution reaction (HER)

The development of affordable alternative energies has gained great interest in recent years. Among them, hydrogen evolution reaction (HER) from water splitting has become of great interest as a source of clean energy. This work aims to develop WS2 synthesized from WO3 prepared by a hydrothermal method assisted by ionic liquid (IL) 1-ethyl-3-methylimidazolium ethyl sulfate [EMIM][EtSO4]), and followed by a heat treatment under nitrogen (N2) atmosphere. Different proportions of IL were used to assess the effect in the WS2 morphology to improve the performance towards the HER in an acidic medium. The resulting compounds were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) with energy dispersive spectroscopy, and electrochemical techniques such as cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and chronoamperometric measurements. WS2 synthesized from WO3 employing IL depicted superior electrocatalytic performance for the HER compared to WS2 prepared without IL. The WS2 sample that involved 2 mL of IL (WS2-2) presented the smaller particle size and the largest crystallite size, two key parameters to perform adequate redox processes: in addition, this sample showed the lowest overpotential value (120 mV), a Tafel slope of 85 mV/dec, and the lowest charge transfer resistance value. These results showed that using the appropriate proportion of ionic liquid as an additive helps to generate smaller WS2 particles, thus generating higher current density, and reducing the overpotential value enhancing the electrocatalytic performance to carry out the HER.

Bifunctional Co3O4/g-C3N4 Hetrostructures for Photoelectrochemical Water Splitting.

This study explored the synergistic potential of photoelectrochemical water splitting through bifunctional Co3O4/g-C3N4 heterostructures. This novel approach merged solar panel technology with electrochemical cell technology, obviating the need for external voltage from batteries. Scanning electron microscopy and X-ray diffraction were utilized to confirm the surface morphology and crystal structure of fabricated nanocomposites; Co3O4, Co3O4/g-C3N4, and Co3O4/Cg-C3N4. The incorporation of carbon into g-C3N4 resulted in improved catalytic activity and charge transport properties during the visible light-driven hydrogen evolution reaction and oxygen evolution reaction. Optical properties were examined using UV-visible spectroscopy, revealing a maximum absorption edge at 650 nm corresponding to a band gap of 1.31 eV for Co3O4/Cg-C3N4 resulting in enhanced light absorption. Among the three fabricated electrodes, Co3O4/Cg-C3N4 exhibited a significantly lower overpotential of 30 mV and a minimum Tafel slope of 112 mV/dec This enhanced photoelectrochemical efficiency was found due to the established Z scheme heterojunction between Co3O4 and gC3N4. This heterojunction reduced the recombination of photogenerated electron-hole pairs and thus promoted charge separation by extending visible light absorption range chronoamperometric measurements confirmed the steady current flow over time under constant potential from the solar cell, and thus it provided the effective utilization of bifunctional Co3O4/g-C3N4 heterostructures for efficient solar-driven water splitting.

A microscopic view on the electrochemical deposition and dissolution of Au with scanning electrochemical cell microscopy – Part II: Potentiostatic dissolution and correlation with in-situ EC-TEM

The electrochemical oxidation of gold nanoparticles (NPs) has been examined in H2SO4 and acidified NaCl by combining multiple techniques including scanning electrochemical cell microscopy (SECCM) and in-situ electrochemical transmission electron microscopy (EC-TEM). Our findings provide novel insights into the intricate oxidation dynamics of Au NPs, which are determined by the interplay between passivation and dissolution. SECCM chronoamperometric measurements in the Cl− containing electrolyte reveal distinct current peak events during the dissolution process. We attribute these events to delayed one-by-one NP dissolution following the rapid breakdown of the passive layer formed during the initial stages of anodic polarization, and exposure of the metallic gold core to Cl− ions. Statistical analysis of these peak events further uncovers relationships between the applied potential and the distribution of the peak descriptors over time. The analysis of the charge consumed during each event indicates that NPs undergo partial dissolution interrupted by rapid re-passivation. As the potential increases, the peak current rises and the duration of the peak events decreases due to intensified dissolution and faster re-passivation. The onset time of the peak events displays a highly stochastic nature. In-situ EC-TEM measurements support these findings by confirming that Au NPs dissolve one-by-one at different time intervals and stages, revealing a core-shell structure during the dissolution process. The shell, which is more resistant, leads to a delayed, particle-by-particle dissolution once it is broken down. Quantification of the EC-TEM video allows recreating an equivalent current-time transient which presents peak events similar to these measured by SECCM. These findings contribute to our understanding of the complex and stochastic behavior of nanoparticle dissolution, which cannot be fully explained by traditional (macro) electrochemistry alone. The combination of SECCM and EC-TEM offers high potential to understand complex nanomaterial degradation pathways, essential for the design of durable electrocatalysts for electrochemical conversion and storage applications.

LaCoO3/SBA-15 as a high surface area catalyst to activate peroxymonosulfate for degrading atrazine in water

An efficient perovskite-based heterogeneous catalyst is highly desired to activate peroxymonosulfate (PMS) for removing organic pollutants in water. A high surface area PMS-activator was fabricated by loading LaCoO3 on SBA-15 to degrade atrazine (ATR) in water. The LaCoO3/SBA-15 depicted better textural properties and higher catalytic activity than LaCoO3. In 6.0 min, atrazine (ATZ) degradation in the selected LaCoO3/SBA-15/PMS system, LaCoO3, adsorption by LaCoO3/SBA-15, sole PMS processes reached approximately 100%, 55.15%, 12.80%, and 16.65 % respectively. Furthermore, 0.04 mg L−1 Co was leached from LaCoO3/SBA-15 during PMS activation by LaCoO3/SBA-15. The LaCoO3/SBA-15 showed stable catalytic activity after reuse. The use of radical scavengers and electron paramagnetic resonance spectroscopy (EPR) demonstrated that ROS such as 1O2, O2•−, •OH, and SO4•− were generated by PMS activated by LaCoO3/SBA-15 owing to redox reactions [Co2+/Co3+, and O2−/O2]. EPR, XPS, ATR-FTIR, EIS, LSV, and chronoamperometric measurements were used to explain the catalytic mechanism for PMS activation. Excellent atrazine degradation was due to high surface area, porous nature, diffusion-friendly structure, and ROS. Our investigation proposes that perovskites with different A and B metals and modified perovskites can be loaded on high surface area materials to activate PMS into ROS.

Unraveling the impact of temperature on the reaction kinetics of the electro-oxidation of methanol on Pt(1 0 0)

Methanol is one of the key molecules in the challenge towards a sustainable future, particularly as a renewable hydrogen carrier fuel and as a low-carbon and net carbon-neutral liquid chemical. For most applications, it is imperative to understand the impact of temperature on the methanol electro-oxidation reaction (MEOR). In this study, the influence of the temperature on the kinetics of the MEOR and the parallel reaction pathways is assessed by investigating responses in both conventional and oscillatory regimes using a single-crystal Pt(100) electrode. Our findings demonstrate that chronoamperometric measurements under steady-state conditions provide more reliable values for apparent activation energies compared to transient conditions. Furthermore, a temperature-dependent shift in the dominance of specific oxidation pathways is observed, analogous to a kinetic and thermodynamic control mechanism, preventing the complete poisoning of the electrode surface. Specifically, oxidation pathways leading to the formation of reaction byproducts predominate at lower temperatures, while the oxidation pathway via COad becomes dominant at temperatures exceeding 30 °C. Moreover, our research shows that, at shorter times, temperature changes minimally affect the mean potential required to sustain the applied current during the oscillations in a galvanostatic experiment, which is closely linked with the voltaic efficiency. However, over longer periods, when mass transport phenomena become significant and mixed-mode oscillations occur, elevated temperatures increase the mean potential, resulting in reduced voltaic efficiency. Therefore, to facilitate the complete conversion of methanol to CO2 without increasing the mean potential for current maintenance, it is essential not only to increase the temperature but also to improve the mass transport conditions to mitigate the mixed-mode oscillations, despite their lower minima reached during oscillation. This idea challenges the conventional assumption that a lower minimum potential implies a lower mean potential during oscillations. This advancement propels our understanding to a more sophisticated level, providing valuable insights to guide the materials design to increase the conversion efficiency and optimize the operating temperature of devices crucial to energy conversion.

Bifunctional Amorphous Transition-Metal Phospho-Boride Electrocatalysts for Selective Alkaline Seawater Splitting at a Current Density of 2Acm-2.

Hydrogen production by direct seawater electrolysis is an alternative technology to conventional freshwater electrolysis, mainly owing to the vast abundance of seawater reserves on earth. However, the lack of robust, active, and selective electrocatalysts that can withstand the harsh and corrosive saline conditions of seawater greatly hinders its industrial viability. Herein, a series of amorphous transition-metal phospho-borides, namely Co-P-B, Ni-P-B, and Fe-P-B are prepared by simple chemical reduction method and screened for overall alkaline seawater electrolysis. Co-P-B is found to be the best of the lot, requiring low overpotentials of ≈270mV for hydrogen evolution reaction (HER), ≈410mV for oxygen evolution reaction (OER), and an overall voltage of 2.50V to reach a current density of 2Acm-2 in highly alkaline natural seawater. Furthermore, the optimized electrocatalyst shows formidable stability after 10,000 cycles and 30h of chronoamperometric measurements in alkaline natural seawater without any chlorine evolution, even at higher current densities. A detailed understanding of not only HER and OER but also chlorine evolution reaction (ClER) on the Co-P-B surface is obtained by computational analysis, which also sheds light on the selectivity and stability of the catalyst at high current densities.

Impact of Surface Chemistry on Emulsion-Electrode Interactions and Electron-Transfer Kinetics in the Single-Entity Electrochemistry.

Single-entity electrochemistry (SEE) provides powerful means to track a single particle, single cell, and even single molecule from the nano to microscale. The electrode serves as not only the detector of collision but also the surface supplier in SEE, and the fundamental understanding of the electrode surface chemistry on the dynamic particle-electrode interactions and electrochemical responses of a single particle still remains unexplored, particularly for soft particles. Herein, dynamic interactions of microemulsions and the interaction-controlled electron-transfer (ET) kinetics are studied employing SEE and fluorescence spectroscopy. The o/w-type nitrobenzene emulsions were prepared with the surfactant-type room temperature ionic liquids (RTILs). Biased the electrode potential for the reduction of 7,7,8,8-tetracyanoquinodimethane within emulsions, it is surprising to see the distinct collision current signals on the carbon fiber ultramicroelectrode (C UME) and Au ultramicroelectrode (Au UME) in the late stage of chronoamperometric measurements. Theoretical understanding was made to determine the ET kinetics behind the disparate current signals. It is believed that the electrode surface chemistry, i.e., the surface energy, has a great influence on the dynamic emulsion-electrode interactions and ET kinetics. On the hydrophilic surface of Au UME, emulsions tend to decompose/detach from the electrode surface immediately after colliding. In contrast, on the lipophilic surface of C UME with lower surface energy, a layer of oil phase accumulated by the coalescence of emulsions and the migration of the precedent colliding emulsions, which would serve as a barrier to block ET via tunneling as manifested by the gradual slowdown of ET rate and the reduced collision frequency in the late stage of measurement. The impacts of the emulsion size and amphiphilicity of RTILs on the C UME-emulsion interactions and ET kinetics were also investigated.

Comparing Commercially Available Gas Diffusion Layers in the Electrochemical CO2 Reduction Reaction

One of the most urgent challenges of our society is the continuously rising level of CO2 in the atmosphere, caused by anthropogenic emission, including different point sources (e.g., cement factories, automobiles, airplanes). The electrochemical CO2 reduction reaction (CO2RR) can be an alternative route for the chemical- and energy industries to convert CO2 into useful products (e.g., carbon monoxide, methane, ethylene), hence providing a value-added approach for CO2 neutralization1.In our work we employed a zero gap electrolyzer cell (active area = 8 cm2), where the catalyst coated electrodes are separated by only a Grade-T Sustainion® X37-50 anion exchange membrane (AEM). As the cathode we used Ag nanoparticle coated gas diffusion layers and as the anode we used Iridium Black coated Ti frit. During the experiments, an anolyte was recirculated continuously through the anode side and humidified CO2 was fed to the cathode side. Beyond the cell structure and membrane, the applied catalyst coated gas diffusion layer (GDL) is one of the most critical elements, determining the efficiency of CO2RR. In this work we compared commercially available GDLs in the CO2RR. All GDLs are used in identical electrochemical cells, under the same experimental conditions2.Our goal was to provide a comprehensive conclusion of the most frequently used commercially available GDLs in CO2RR. We studied the effect of the microporous layer (MPL), the PTFE content, the thickness, and the structure of the selected GDLs. One-hour long chronoamperometric measurement revealed some trends and important differences - in case of five of the tested GDLs (Sigracet 28BC, Sigracet 39BB, Freudenberg H23C6, Toray H60 MPL and Elat LT 1400W), the CO partial current density exceeded 500 mA cm−2 already at 3.0 V cell voltage. To unravel which structural parameters affect the electrolyzer performance the most, the results were compared along a few selected properties (Figure 1.): (A) whether they contained MPL or not, (B) the PTFE content, (C) the overall thickness, and (D) the structure of the GDL.<Figure 1.> Figure 1. Comparing commercially available gas diffusion layers in the CO2RR. Partial current densities for CO and H2 production during one-hour long chronoamperometric CO2RR measurements at ΔU = 3.0 V, applying different GDL based cathode GDEs with Ag catalyst. The electrolyte solution was 0.1 M CsOH, humidified CO2 was fed to the cathode at a flow rate of 12.5 cm3 cm−2 min−1 and the temperature of the electrolyzer cell was 60 °C. The error bars represent the deviations of two consecutive analyses during the same measurements.Long-term electrolysis experiments (100 hours) were performed with two GDLs, the Sigracet 39BB and the Toray H60 MPL. Throughout the long-term electrolysis, a stable total current density and CO formation selectivity was measured in both cases. Throughout our study, to understand the differences among their electrochemical behavior, of the various GDLs, we characterized their wetting properties and microstructure before the electrochemical measurements. The structure and morphology of the GDLs were characterized with SEM, micro-CT and contact angle measurements. References (1) Samu, A. A.; Kormányos, A.; Kecsenovity, E.; Szilágyi, N.; Endrödi, B.; Janáky, C. Intermittent Operation of CO2 Electrolyzers at Industrially Relevant Current Densities. ACS Energy Lett. 2022, 1859–1861(2) Samu, A. A.; Szenti, I.; Kukovecz, Á.; Endrődi, B.; Janáky, C. Systematic Screening of Gas Diffusion Layers for High Performance CO2 Electrolysis. Commun. Chem. 2023, 6 (1), 1–9 Supported by the KDP-2021 program of the Ministry for Innovation and Technology from the source of the National Research, Development and Innovation fund. Figure 1

Architecture design of TiO2 with Co-doped CdS quantum dots photoelectrode for water splitting.

Photoelectrochemical hydrogen production is a critical key to solving the carbon-zero goal of countries due to renewable sources of solar light and combustion products of hydrogen-only water. Here, an architecture design for an n-type nano rosettes-rod TiO2 (RT) surface using CdS and Co-doped CdS quantum dots (QDs) is carried out utilizing the SILAR (simple ionic layer adsorption and reaction) method. Furthermore, the photocatalytic behaviour of Co-doped CdS QDs SILAR cycles deposition is investigated in various cycles, including 5, 8, 10, and 12. The FESEM, Raman XRD, Uv-Vis spectrometer, and vibration modes are used to evaluate the photoelectrode surface structure, crystal structure, and solar light absorption, respectively. FESEM images and XRD pattern revealed successive CdS QDS and Co-doped CdS QDs deposition on the RT boundary and rising SILAR cycles of Co-doped CdS QDs lead to further coverage of RT surface. UV-vis spectrometer indicated shifting solar light absorption to the visible region by applying more SILAR cycles of Co-doped CdS QDs deposition. The electrochemical parameters obtained from EIS showed total polarization resistance (Rp) of the RT electrode dramatically decreased with 10 SILAR cycle Co-doped CdS QDs deposition (5093 Ω cm2 and 617 Ω cm2). Linear sweep voltammetry (LSV) and chronoamperometric photocatalytic performance measurements indicated Co-doped CdS QDs on RT extremely enhanced photoresponse under solar irradiation and 10 SILAR cycle Co-doped CdS QDs improved photocurrent density about fourfold according to blank RT electrode.

Unleashing the power of solar light: WO3 nanorods decorated onto BiVO4 dendrites for tetracycline detoxification and water splitting.

The coupling of different oxide materials in a nanohybrid enables the customization of their optical and charge transport properties, leading to improved interfacial charge segregation and migration. In this study, BiVO4/WO3 (BVW), a sunlight-driven photocatalyst with distinct mole ratios was synthesized via a facile hydrothermal approach. The resultant catalyst exhibits a nanorods shape morphology decorated onto dendrite-like matrix and is studied for photocatalytic elimination of tetracycline (TC) and photoelectrocatalytic (PEC) H2 production. The effect of illumination time, solution pH, photocatalyst concentration, and mole ratios of BiVO4 to WO3 on the photocatalytic abatement of TC were tested sequentially as effective operating factors. Under optimal condition, 3:1 BiVO4:WO3 (31BVW) nanohybrid demonstrated a maximum degradation efficacy of 96.2% (rate constant ~0.0241 min-1), which is much better than its individual components and commercial TiO2-P25 (50.9%). The resultant by-products of TC decomposition were analyzed using GC-MS to explain the degradation mechanism. Moreover, as a photoanode, 31BVW showed a high photocurrent density of 0.64 mA/cm2 at 1.23 V vs RHE and a steady photocurrent for ~6 h under chronoamperometry study at1.23 V vs RHE. However, bare BiVO4 and WO3 exhibited the photocurrent density of 0.001 mA/cm2, and 0.015 mA/cm2, respectively at 1.23 V vs RHE. The Mott-Schottky analysis of 31BVW confirms their n-type behavior, with a calculated flat band potential of -0.067 V. The hydrogen production rate was theoretically calculated as 4.56 mmolcm-2 s-1 from chronoamperometric measurements. The photocatalyst's efficacy in TC degradation was further established via its reusability upto 7 cycles. Post degradation characterization of catalyst confirms its stability in lieu of practical usage. Comparative studies with existing literature revealed the superiority of reported photocatalysts in both applications. Overall, the binary BVW photocatalyst shows great potential for removing detrimental contaminants as well as H2 production via PEC water splitting due to efficient charge separation, reduced recombination, high surface area, and widen absorption window of the nanohybrid.

Exploring Stable and Selective Anode Materials for the Electrochemical Oxidative Coupling of Methane (EOCM): A Case Study of Doped Titanates

The development of next-generation solid oxide fuel cells (SOFCs) relies on integrating materials such as La0.6Sr0.4Co0.2Fe0.8O3- δ (LSCF), which has been lauded for its fast oxygen ion and electron conduction, along with its high oxygen reduction activity.[1] However, the use of LSCF has been plagued by 1) stability issues caused by surface Sr precipitation and 2) subsequent poisoning by Cr- or S- containing species.We have previously shown that the introduction of more oxidizable cations at the electrode surface can effectively improve both the stability and the oxygen exchange kinetics of the electrodes. However, the influence of these cations, as with many dopant infiltration studies, is currently not fully understood across all possible modes of electrode surface stabilization/activity enhancement. For example, we have recently discovered that at 800°C and under air atmospheres (i.e. at typical SOFC operational conditions), these Hf/Zr surface cation dopants are mobile and diffuse into the lattice of a porous LSCF electrode as evidenced by their vanishing x-ray photoelectron signals. This is accompanied nevertheless by a noticeable electrode stabilization, suggesting a sub-surface effect of the introduced dopants.Inspired by this, in this work our aim is to uncover the mechanism responsible for the stabilization of the surface oxygen exchange kinetics. Our approach involves dense thin film LSCF as model system to investigate the temperature-dependent physicochemical properties of these surface and sub-surface dopant cations. We fabricate LSCF thin films via pulsed laser deposition onto single crystalline substrates and then introduce our targeted cations at the surface via an aqueous solution infiltration. We characterize the electrochemical performance of the thin films by performing chronoamperometric and impedance spectroscopic measurements to discern the extent of the temporal electrode performance degradation using metrics such as area-specific resistance. In parallel, we aim to rationalize the observed electrochemical performance stabilization using complementary surface science techniques. We propose investigating the cation dissolution phenomenon through a combination of x-ray photoelectron and Auger electron spectroscopies, along with atomic force microscopy, scanning/transmission electron microscopy, scanning tunnelling microscopy and grazing incidence thin film x-ray diffraction. This study aims to reveal the influence of sub-surface more oxidizable cations on the extent of Sr segregation and highlights how two major factors contribute to the observed trends: Electrode fabrication conditions, for example the dopant concentration dependence (insufficient or excessive surface dopant concentrations has previously been shown to suppress the stabilization effect).[3]Electrode operation conditions, for example the temperature profile experienced by the cell (higher temperatures lead to dopant dissolution). [1] SP Jiang, Int. J. Hydrogen Energy 44 (14), 7448 (2019).[2] N Tsvetkov et al., Nature Mat. 15 (9), 1010 (2016).[3] N Tsvetkov et al., Faraday Disc. 182 (0), 257 (2015).

Magnetically-Induced Buoyancy for Efficient Electrochemical Oxygen Production in Microgravity

The realization of long-term space travels and the establishment of a lunar research platform are challenged by the lack of technological device architectures for efficient, stable and continuous oxygen production. One obstacle is that the near-absence of buoyancy in microgravity results in hindered gas bubble desorption at the electrode-electrolyte interface, causing lower efficiencies for electrolyser systems when operating in space.1,2 The significantly reduced buoyancy force also has severe complications for phase separation, which is a crucial process for a variety of space technologies also including heat transfer, fuel production and removal of carbon dioxide from cabin air. Multiple approaches have been studied in the past to induce phase separation such as creating centrifugal force fields. These approaches lack however efficiency, stability and robustness.3,4 In our recent work, we demonstrate the use of magnetic polarisation to artificially induce buoyancy in the electrolytic oxygen evolution half-cell reaction and thus significantly increasing the overall half-cell efficiency. This was carried out in a series of experiments at the Bremen Drop Tower, Center of Space Technology and Microgravity (ZARM, Germany), where short-term microgravity conditions of 9.2 s were achieved.5,6. Chronoamperometric and cyclic voltammetry measurements on high-activity RuOx electrocatalyst structures on a Ti substrate were undertaken with and without a magnet in close proximity to the electrode to closely monitor the electrochemical performance in a three-electrode potentiostatic arrangement and to demonstrate the magnetic effect on gas bubble desorption during free fall. It was observed that current densities for the electrodes at a potential of +1.49 V vs RHE were significantly higher in the presence of a magnet. We conclude that magnetic phase separation can be utilised in electrolytic systems in reduced gravitational environments to efficiently detach oxygen bubbles from the electrode surface and operate the devices at higher efficiencies, providing a key advancement for future oxygen production in space missions.2,3,5 References Cheng, W.-H.; Richter, M. H.; May, M. M.; Ohlmann, J.; Lackner, D.; Dimroth, F.; Hannappel, T.; Atwater, H. A.; Lewerenz, H.-J. (2018). Monolithic Photoelectrochemical Device for Direct Water Splitting with 19% Efficiency. ACS Energy Lett., 3, 1795−1800.Saravanabavan, S.; Coulthard, C. T.; Kaur, M.; Brinkert, K. (2022). Catalysis in Space Environments. doi.org/10.1002/9783527830909.ch7 In: Hessel V., Stoudemire J., H. Miyamoto & I. D. Fisk (Eds.). In Space Manufacturing and Resources.Wiley-VCH. ISBN: 978-3-527-83091-6Romero-Calvo, Á.; Akay, Ö.; Schaub, H.; Brinkert, K. (2022). Magnetic phase separation in microgravity. npj Microgravity 8 (32). doi.org/10.1038/s41526-022-00212-9.Harvey, A.; Ramshaw, C.; Reay, D. A. Process Intensification: Engineering for Efficiency. Sustainability and Flexibility. 2nd edition. Butterworth- Heinemann; 201Brinkert, K.; Richter, M. H.; Akay, Ö.; Liedtke, J.; Giersig, M.; Fountaine, K. T.; Lewerenz, H. J. (2018). Efficient solar hydrogen production in microgravity environment. Commun. 9(2527). doi: 10.1038/s41467-018-04844-yhttps://www.zarm.uni-bremen.de/fileadmin/user_upload/drop_tower/Users_Manual_0412.pdf

Crosslinked Hyperbranched Polyglycerol-Based Polymer Electrolytes for Lithium Metal Batteries

Tailored partially methylated and methacrylated hyperbranched polyglycerols (hbPG-MAx/OMey) combined with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as conducting salt were investigated after crosslinking with respect to their application as solid polymer electrolytes (SPE) in lithium metal batteries. For sample preparation and coating, a straightforward solvent-free photopolymerization method was applied. With the aim of finding the right balance between mechanical and electrochemical properties, electrolytes with different crosslinking densities were studied. High crosslink density increases mechanical integrity but reduces local chain motion and thus ionic conductivity at the same time. Differential scanning calorimetry (DSC), chronoamperometric and impedance measurements show that the hyperbranched polyether structure interacts strongly with lithium cations. Finally, the SPE with the lowest crosslinking density was selected and investigated in cycling tests due to the parameters of highest absolute values in conductivity (2.1 × 10−6 S cm−1 at 30 °C; 2.0 × 10−5 S cm−1 at 60 °C), lowest Tg (from DSC: −39 °C), electrochemical stability window (4.3 V vs. Li/Li+) and mechanical strength (1.6 ± 0.4 MPa at 25 °C). At low C-rates and elevated temperatures (60 °C), cells were cycled with high Coulombic efficiency. At high C-rates, a distinct decrease in specific capacity was observed due to insufficient ionic conductivity.

Towards the design of mechanical flexible electrodes for sensing: Self-standing polypyrrole-copper nanocomposites

Self-standing electrodes with intrinsic conductivity and high electrocatalytic activity emerge as an alternative to existing sensors given their promising flexibility and wearability. Herein we demonstrate the fabrication of flexible sensors based on a hybrid nanocomposite of self-supported polypyrrole electrodes modified with copper nanoparticles (PPy-Cu) for the electrochemical detection of dopamine. The surface morphology and composition of flexible nanocomposite electrodes was studied using scanning electron microscopy (SEM), in combination with elemental mapping through energy dispersive X-ray spectroscopy (EDS). Surface characterization by X-ray photoelectron spectroscopy (XPS) revealed that copper exists in both Cu(0) and Cu(II) forms. The incorporation of copper nanoparticles in the self-standing polypyrrole matrix introduced additional electroactive sites, further enhancing charge transfer, and improving the device's sensitivity. The sensing capability of self-standing PPy-Cu electrodes was evaluated using chronoamperometric measurements and optimized at various copper electrodeposition times. PPy-Cu 120s showed great performance for dopamine sensing with a low limit of detection of 1.19 μM and a linear range of 2.5 μM–250 μM. Additionally, the self-standing sensor is comprised entirely of Polypyrrole, a biocompatible polymer, and Copper nanoparticles, making it sustainable and environmentally friendly. These encouraging results pave the way for the development of next-generation flexible sensors for the detection of neurotransmitters and environmentally relevant analytes.

Fullerene-based mimics of enhanced acetylcholine detection for the diagnosis of Alzheimer’s disease

The design of sensitive and cost-effective enzyme-free sensor systems for the effective electrooxidation of acetylcholine (ACh) plays a key role in following up on Alzheimer’s disease. We report a fullerenzyme-based catalyst (F-HS) for the electrochemical detection of ACh that mimics enzymatic active sites using multifunctional self-assembled nanostructures. As a proof-of-concept, histidine and serine amino acid-based functionalization of fullerenzymes was used, along with embedded nickel ions (F-HS-Ni), which tend to coordinate with the nitrogen of the imidazole ring of the histidine moiety. Further, the electrode modifier properties of the resulting material were examined for sensor applications. Enhanced cyclic voltammetry and chronoamperometric measurements affirmed that the F-HS-Ni material displayed the most prominent activity for the electrocatalytic oxidation of ACh, allowing an amperometric response in a linear range of ACh concentrations of 20–6000 μM with a low detection limit of 8.01 μM. Furthermore, the platform allows for the detection of ACh with a good rate of recovery in human serum samples, offering a good potential method for the quick detection and diagnosis of Alzheimer’s.

Development of an electrochemical DNA-based biosensor for the detection of the cardiovascular pharmacogenetic-altering SNP CYP2C9*3

Cardiovascular diseases are among the major causes of mortality and morbidity. Warfarin is often prescribed for these disorders, an anticoagulant with inter and intra-dosage variability dose required to achieve the target international normalized ratio. Warfarin presents a narrow therapeutic index, and due to its variability, it can often be associated with the risk of hemorrhage, or in other patients, thromboembolism. Single-nucleotide polymorphisms are included in the causes that contribute to this variability. The Cytochrome P450 (CYP) 2C9*3 genetic polymorphism modifies its enzymatic activity, and hence warfarin's plasmatic concentration. Thus, the need for a selective, rapid, low-cost, and real-time detection device is crucial before prescribing warfarin. In this work, a disposable electrochemical DNA-based biosensor capable of detecting CYP2C9*3 polymorphism was developed. By analyzing genomic databases, two specific 78 base pairs DNA probes; one with the wild-type adenine (Target-A) and another with the cytosine (Target-C) single-nucleotide genetic variation were designed. The biosensor implied the immobilization on screen-printed gold electrodes of a self-assembled monolayer composed by mercaptohexanol and a linear CYP2C9*3 DNA-capture probe. To improve the selectivity and avoid secondary structures a sandwich format of the CYP2C9*3 allele was designed using complementary fluorescein isothiocyanate-labeled signaling DNA probe and enzymatic amplification of the electrochemical signal. Chronoamperometric measurements were performed at a range of 0.015–1.00 nM for both DNA targets achieving limit of detection of 42 p.m. The developed DNA-based biosensor was able to discriminate between the two synthetic target DNA targets, as well as the targeted denatured genomic DNA, extracted from volunteers genotyped as non-variant homozygous (A/A) and heterozygous (A/C) of the CYP2C9*3 polymorphism.

RGO decorated N-doped NiCo2O4 hollow microspheres onto activated carbon cloth for high-performance non-enzymatic electrochemical glucose detection

This paper reports the first effective fabrication of a high-performance non-enzymatic glucose sensor based on activated carbon cloth (ACC) coated with reduced graphene oxide (RGO) decorated N-doped urchin-like nickel cobaltite (NiCo2O4) hollow microspheres. Hierarchically mesoporous N-doped NiCo2O4 hollow microspheres were synthesized using a facile solvothermal method, followed by thermal treatment in a nitrogen (N2) atmosphere. Subsequently, they were hydrothermally decorated with RGO nanoflakes. The resulting composite was dip-coated onto ACC, and its electrochemical and glucose sensing performances were investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and chronoamperometric measurements in a three-electrode system. The composite electrode sensor demonstrates admirable sensitivity (6122 μM mM−1 cm−2) with an ultralow detection limit (5 nM, S/N = 3), and it performs well within a substantial linear range (0.5–1.450 mM). Additionally, it exhibits good long-term response stability and outstanding anti-interference performance. These outstanding results can be attributed to the synergistic effects of the highly electrically conductive ACC with multiple channels, the enhanced catalytic activity of highly porous N-doped NiCo2O4 hollow microspheres, and the large electroactive sites provided by its well-developed hierarchical nanostructure and RGO nanoflakes. The findings highlight the enormous potential of the ACC/N-doped NiCo2O4@RGO electrode for non-enzymatic glucose sensing.

Influence of Fibroin Membrane Composition and Curing Parameters on the Performance of a Biodegradable Enzymatic Biosensor Manufactured from Silicon‐Free Carbon

Herein, fibroin, polylactide (PLA), and carbon are investigated for their suitability as biocompatible and biodegradable materials for amperometric biosensors. For this purpose, screen‐printed carbon electrodes on the biodegradable substrates fibroin and PLA are modified with a glucose oxidase membrane and then encapsulated with the biocompatible material Ecoflex. The influence of different curing parameters of the carbon electrodes on the resulting biosensor characteristics is studied. The morphology of the electrodes is investigated by scanning electron microscopy, and the biosensor performance is examined by amperometric measurements of glucose (0.5–10 mM) in phosphate buffer solution, pH 7.4, at an applied potential of 1.2 V versus a Ag/AgCl reference electrode. Instead of Ecoflex, fibroin, PLA, and wound adhesive are tested as alternative encapsulation compounds: a series of swelling tests with different fibroin compositions, PLA, and Ecoflex has been performed before characterizing the most promising candidates by chronoamperometry. Therefore, the carbon electrodes are completely covered with the particular encapsulation material. Chronoamperometric measurements with H2O2 concentrations between 0.5 and 10 mM enable studying the leakage current behavior.

A Microporous Bifunctional Electrochromic Energy‐Storage Polymer of Thiophene, Triphenylamine, and Thienothiophene

The novel monomer, 4‐(2‐(4‐(bis(4‐(thiophen‐2‐yl)phenyl)amino)phenyl)‐5‐(thiophen‐2‐yl)thieno[3,2‐b]thiophen‐3‐yl)benzonitrile, is synthesized by applying Suzuki coupling reaction and electropolymerized directly onto indium tin oxide coated glass electrode surface to obtain a conjugated microporous polymer of [Th3CNTT–TPA] (P[Th3CNTT–TPA]). The morphology and structure of the polymer film are characterized by atomic force microscopy, Fourier transform infrared, and UV–visible spectroscopies. Electrochemical properties are studied using cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic charge–discharge, and chronoamperometric measurements. Its gravimetric capacity and capacitance values are measured to be 65 and 235 F g−1 at a current density of 3 A g−1, respectively. It shows high energy and power densities of 65 and 32.5 kWh kg−1, respectively, and exhibits high coloration efficiency of 513 C−1 cm2 in visible region, switching between yellow and grey colors. Three different electrochromic–supercapacitor devices, that is, one symmetrical (energy storage device (ESD)1) and two asymmetrical, using poly(3,4‐ethylendioxythiophen) (ESD2) and poly(3,4‐propylenedioxypyrrole) (ESD3) as counter electrodes, are fabricated. The asymmetrical device, ESD3, demonstrats better capacity and stability. Regarding the cyclic stability and electrochromic‐energy‐storage properties, P[Th3CNTT–TPA] can be considered as a good candidate for multifunctional applications.