Electrochemical Switching Research Articles

Electrochemical Switching of Electromagnetism by Hierarchical Disorder Tailored Atomic Scale Polarization.

High-frequency electronic response governs a broad spectrum of electromagnetic applications from radiation protection, and signal compatibility, to energy recovery. Despite various efforts to manage electric conductivity, dynamic control over dielectric polarization for real-time electromagnetic modulation remains a notable challenge. Herein, an electrochemical lithiation-driven hierarchical disordering strategy is demonstrated for actively modulating electromagnetic properties. The controllable formation and diffusion of coherent interfaces and cation vacancies tailor the coupling of atomic electric field and thus the locally polarized domains, which leads to the reversible electromagnetic transparency/absorption switching with a tunable range of -0.8--20.4 dB for the reflection loss and a broad operation bandwidth of 4.6 GHz. Compared to traditional methods of heteroatomic doping, hydrogenation, mechanical deformation, and phase transition, the electrochemical strategy shows a larger regulation scope of dielectric permittivity with the maximum increase ratios of 260% and 1950% for real and imaginary parts, respectively. This enables the construction of various device architectures including the adaptive window and pixelated metasurface. The results offer opportunities to achieve intelligent electromagnetic devices and pave an avenue to rejuvenate various electromagnetic functions of semiconductive oxides.

Development of an Activity-Based Ratiometric Electrochemical Switch for Direct, Real-Time Sensing of Pantetheinase in Live Cells, Blood, and Urine Samples.

Pantetheinase is a key biomarker for the diagnosis of acute kidney injury and the monitoring of malaria progression. Currently, existing methods for sensing pantetheinase, also known as Vanin-1, show considerable potential but come with certain limitations, including their inability to directly sense analytes in turbid biofluid samples without tedious sample pretreatment. Here, we describe the first activity-based electrochemical probe, termed VaninLP, for convenient and specific direct targeting of pantetheinase activity in turbid liquid biopsy samples. The probe was designed such that cleavage of the pantetheinase amide linkage, triggered by a self-immolative reaction, simultaneously ejects an amino ferrocene reporter. Among the distinctive properties of the VaninLP probe for sensing pantetheinase are its high selectivity, sensitivity, and enzyme affinity, a wide linear concentration range (8-300 ng/mL), and low limit of detection (2.47 ng/mL). The designed probe precisely targeted pantetheinase and was free of interference by other electroactive biological species. We further successfully applied the VaninLP probe to monitor and quantify the activity of pantetheinase on the surfaces of HepG2 tumor cells, blood, and urine samples. Collectively, our findings indicate that VaninLP holds significant promise as a point-of-care tool for diagnosing early-stage kidney injury, as well as monitoring the progression of malaria.

One-pot Functionalization for the Preparation of Cobaltocene-Modified Redox-Responsive Porous Microparticles.

Porous organic cobaltocenium-containing particles are scarce in literature but highly interesting for their electrochemical properties and reusability in, for example, catalysis or magnetic systems. In this work, we present a scalable one-pot strategy to introduce tailorable amounts of cobaltocenium on a porous substrate, adjusting the electrochemical switching capability. For this purpose, 3-(triethoxysilyl)propan-1-amine (APTES) and ethynyl cobaltocenium hexafluorophosphate is used as functionalization agents for in-situ catalyst-free hydroamination, followed by silane condensation at the particles' surface. Functionalized particles are characterized by attenuated total reflection infrared spectroscopy (ATR-IR), thermogravimetric analysis (TGA), laser scanning confocal microscopy (LSCM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), inductively coupled plasma mass spectrometry (ICP-MS), powder X-ray diffraction (PXRD) and cyclic voltammetry (CV) showing excellent control over the degree of functionalization, i. e., the added cobaltocenium reagents. The electrochemical stability and good addressability while preserving the porous structure are shown. By utilizing higher amounts of APTES, the overall cobaltocenium amount can be reduced in favor of additional amine groups, strongly affecting the electrochemical behavior, making this functionalization strategy a good platform for metallopolymer immobilization and tailored functionalization. Additionally, thermal treatment of the synthesized metallopolymer microparticles paves the way to magnetic properties with tailorable microporous architectures for end-of-life and upcycling aspects.

Activating Ga0.8Ti0.4Nb0.8O4 cathode for direct electrolysis of CO2via electrochemical switching and infiltration of co-catalyst

Solid oxide electrolysis cell (SOEC) can efficiently convert CO2 into CO using renewable energy sources. SOECs that operate at around 800 °C and negative bias for CO2 reduction pose demanding requirements on the stability of the cathode. Here, a non-perovskite niobate, Ga0.8Ti0.4Nb0.8O4 (GTN), is developed as a robust cathode that can be activated under a −1.4 V bias at 800 °C for CO2 splitting. A gradual increase in the current density of the electrolysis cell with GTN cathode is accompanied by the partial reduction of Nb5+ to Nb4+ to produce NbO2 and a pseudorutile phase. The coupling of NbO2 nanoparticles and the defective pseudorutile surface layer serves as a good combination for the electrochemical reduction of CO2 at elevated temperatures: the electrolysis performance is slightly enhanced by ionic infiltration of Ni because the in situ grown metallic NbO2 can serve as the electron reservoir, similar to the metal Ni. The presence of CeO2 can increase the activation of CO2 and provide the ionic transport between the interface of the electrolyte and cathode. This work demonstrates a robust niobate that can be reduced by electrochemical switching to reduce the stubborn Nb5+ to produce a composite functional layer for efficient CO2 splitting.

Solid-State Electrochemical Thermal Switches with Large Thermal Conductivity Switching Widths.

Thermal switches that switch the thermal conductivity (κ) of the active layers are attracting increasing attention as thermal management devices. For electrochemical thermal switches, several transition metal oxides (TMOs) are proposed as active layers. After electrochemical redox treatment, the crystal structure of the TMO is modulated, which results in the κ switching. However, the κ switching width is still small (<4W m-1 K-1). In this study, it demonstrates that LaNiOx-based solid-state electrochemical thermal switches have a κ switching width of 4.3W m-1 K-1. Fully oxidized LaNiO3 (on state) has a κ of 6.0W m-1 K-1 due to the large contribution of electron thermal conductivity (κele, 3.1W m-1 K-1). In contrast, reduced LaNiO2.72 (off state) has a κ of 1.7W m-1 K-1 because the phonons are scattered by the oxygen vacancies. The LaNiOx-based electrochemical thermal switch is cyclable of κ and the crystalline lattice of LaNiOx. This electrochemical thermal switch may be a promising platform for next-generation devices such as thermal displays.

Expanding Color Control of Anodically Coloring Electrochromes Based on Electron-Rich 1,4-Dihydropyrrolo[3,2-b]pyrroles.

Anodically coloring electrochromes have received attention in recent years as high-contrast alternatives to cathodically coloring electrochromes due to their superior optical contrast during electrochemical switching. While current systems represent significant progress for organic electrochromics, it is necessary to expand the structural diversity of these materials while simultaneously reducing the hazards associated with synthetic protocols. With these considerations in mind, a family of 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) chromophores with varying functionalities along the 2,5-axis was envisioned to accomplish these goals. After predicting different absorbance traits as oxidized molecules with time-dependent density functional theory, DHPP chromophores with varying peripheral functionalities were synthesized in a single aerobic synthetic step via an iron-catalyzed multicomponent reaction and characterized as high-contrast chromophores. In solution, the DHPP chromophores absorb in the ultraviolet region of the electromagnetic spectrum, resulting in color-neutral L*a*b* color coordinates of ∼100, 0, 0. Upon chemical oxidation, each molecule transitions to absorb at various points across the visible spectrum based on the extent of electron-donating ability and can display five distinct colors. Importantly, the chromophores are redox-active and display switching capabilities with an applied electrochemical potential. In conjunction with building fundamental insights into molecular design of DHPP chromophores, the results and synthetic simplicity of DHPPs make them compelling materials for color-controlled high-contrast electrochromes.

A Gd-doped ceria/TiOx nanocomposite as the active layer in a three terminal electrochemical resistivity switch.

Coupling between an electrochemical reaction and a functional material property has been termed electro-chemo-X, or EC-X, where X can refer to mechanical, optical, magnetic or thermal properties. Recently, our group has demonstrated a two-terminal electro-chemo-mechanical (ECM) membrane actuator operating under ambient conditions and containing a Ce0.8Gd0.2O1.9 solid electrolyte layer sandwiched between two Gd-doped ceria/TiOx nanocomposite thin films. Reducing one nanocomposite film while oxidizing the other was observed to produce reversible volume change thereby driving membrane actuator operation. Here, we use the same electrolyte and nanocomposite layer pair (the upper one as the ion reservoir and the lower, as the active layer) to further explore the EC-X effect. We demonstrate the suitability of the nanocomposite for a three-terminal, thin film-based resistivity switch. We find that application of ±6 V (<60 kV/cm) bias to the gate terminal for two hours under ambient conditions changes the nanocomposite conductivity in the channel between the source and drain by at least 40%. When the bias is negative, the active layer remains in a more highly conductive state for approximately twenty-four hours. Impedance spectroscopy and cyclic voltammetry reveal oxygen ion migration taking place between the active layer and the reservoir. X-ray photoelectron spectroscopy indicates that, in the absence of negative gate bias, thermal oxidation of Ce+3 - > Ce+4 is similarly effective in leading to increased nanocomposite conductivity, while reduction produces the opposite effect. With the expectation that the response time can be significantly shortened, the proposed resistivity switch may be suitable for future applications such as sensors, neuromorphic computing or spintronics.

Electrochemically responsive nanofibers by stimulation of a dialkyl-bipyridinium molecular switch

The translation of the well-known reversible electrochemical switching of viologen species from solution to the solid state may open enormous possibilities for developing electrically responsive materials. In this work, we present and discuss the electrochemical response of a viologen derivative, 1,1′-dipropyl-4,4′-bipyridinium bis-hexafluorophosphate (Bpy2+), embedded into a polyurethane fibrous matrix. The results showcase the possibility of stimulating electrochemically the active molecule inside the polymer fibers, both in random and aligned configurations, retaining the fibrous morphology and structure while avoiding the use of conductive polymers and ionic liquids, thus opening a new scenario in electrochemically responsive soft actuators.

Influence of active electrode impurity on memristive characteristics of ECM devices

Memristive devices are promising candidates for the implementation in more than Moore applications. Their functionalities, electrical characteristics, and behavior, such as high scalability and stability at extreme conditions such as low/high temperatures, irradiation with electromagnetic waves and high-energy particles, and fast operation are required for solving current problems in neuromorphic architectures. Electrochemical metallization (ECM)-based memristive devices are among the most relevant in this scenario owing to their low power consumption, high switching speed, showing high HRS/LRS resistance ratio in digital mode, and as well multilevel to analogue-type performance, allowing to be used in wide spectrum of applications, including as artificial neurons and/or synapses in brain-inspired hardware. Despite all the advantages and progressing industrial implementation, effects of materials selection and interactions are not sufficiently explored, and reliable design rules based on materials approach are still to be formulated by the correct choice of structures and materials combinations to ensure desired performance. In this work, we report on the effects of impurities in the copper active electrode on the electrical characteristics of Cu/Ta2O5/Pt ECM devices. The results demonstrate that Cu impurity is modulating the electrochemical behavior and switching speed due to different catalytic activity and redox reaction rates. In addition, stability and variability are improved by decreasing the number of foreign atoms. Our results provide important additional information on the factors needed to be considered for rational device design.

A PEDOT based graft copolymer with enhanced electronic stability.

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) remains the most investigated conjugated polymer in bioelectronics, due to its biocompatibility, high conductivity, and commercial availability. Despite these advantages, it suffers from structural and electronic instability, associated with the PSS component. Here, a graft copolymer based on ionised sulfonic modified PEDOT, poly(EDOTS-g-EDOT), was electrochemically synthesised with demonstrated structural and electronic stability and enhanced electrochemical performance. The graft copolymer was insoluble in water without crosslinking, and exhibited enhanced ion diffusion upon electrochemical switching, as revealed by its volumetric capacitance (159 ± 8 F cm-3), which was significantly higher than that of spin-coated PEDOT:PSS films (41 ± 5 F cm-3). Similarly, its performance as an active channel material in organic electrochemical transistors (OECTs) was superior to the spin-coated PEDOT:PSS, as shown for instance by its high normalised transconductance (273 ± 79 S cm-1) and a significantly high ION/IOFF ratio (19 345 ± 1205). Its short- and long-term electronic stability were also confirmed with no drop in its output drain current, despite its high swelling degree. In contrast, the spin-coated PEDOT:PSS experienced a significant deterioration in its performance over the same operational time. The facile synthesis and improved performance of poly(EDOTS-g-EDOT) highlight the importance of innovative material design in overcoming existing operational shortcomings in electronic devices.

Electrochemical switching in mechanically interlocked molecules (MIMs)

Mechanically interlocked molecules (MIMs) which include rotaxanes and catenanes are formed by the mechanical linking of two or more components and has the ability to switch between different states in the presence of an external stimuli.

Electrochemical exsolution of metal nanoparticles from perovskite oxide upon electrolysis

This study presents a comprehensive investigation into the electrochemical reduction of LSCF perovskite during electrolysis, aiming to understand the exsolution of metal nanoparticles. The exsolution of metal nanoparticles from perovskite electrodes can significantly enhance their electrochemical performance in electrolysis. By applying cathodic polarization to the perovskite oxide electrode, the exsolution process was shown to be electrochemically induced within a few minutes. Additionally, a user-designed X-ray absorption spectroscopy operando cell was employed to analyze the edge energy change of the B-site atoms during electrolysis. The electrochemical reduction of perovskite and the subsequent exsolution of the B-site metal nanoparticles were investigated by scanning the cell voltage, providing an understanding of the electrochemical behavior during electrolysis. The electrochemical switching point, characterized by a decrease in the incremental area-specific resistance, was identified. This study offers valuable insights into the electrochemical exsolution process of metal nanoparticles from perovskite oxide electrodes.

Chiroptical Switching of Electrochromic Polymer Thin Films.

The interaction between light and chiroptical polymers plays a crucial role in chiroptics, spintronics, and chiral-spin selectivity. Despite considerable successes in creating dissymmetric polymer films, the elucidation of chiroptical activities under electrochemical switching remains unexplored. Here homogeneous chiral electrochromics is reported using chiral assembly of conjugated polymers through a transient solidification process with molecular chiral templates. In their neutral state, the chiral electrochromic polymers directly produce a remarkably dissymmetric polarization-dependent transmittance. The circular dichroism (CD) and dissymmetric transmission can be tuned by adjusting the doping level of the electrochemically active polymer films. Under high levels of oxidation, the chiroptical activities are reversed with strong bleaching in the visible, leading to formation of monosignate CD spectra over the infrared region. The matching between circular polarization handedness and chirality of chiroptical polymers makes a distinct impact on optical contrast and color switching dynamics due to the flipped chiroptical activities through polymer redox reactions. The differential circularly polarized transmission in the chiral see-through display can make a well-resolved color change in human eyes, demonstrating proof-of-concept devices for 3D imaging and information encryption. This work serves as a foundation to develop advanced on-chip fabrication of circular polarization-multiplexed display in flexible and highly integrated platforms.

Fluorescent Switchable Surfaces Based on Quantum Dots Modified With Redox‐Active Molecules

AbstractBy combining the switching ability of redox molecules with the unique fluorescence properties of quantum dots (QDs), a robust electrochemical fluorescence switch is developed here. This is realized by grafting CdSe/ZnS QDs on transparent indium tin oxide (ITO) substrates and, subsequently, modifying them with a Ferrocene (Fc) molecular monolayer. The application of oxidation/reduction voltage pulses to tune the Fc redox state leads to the tuning of the surface fluorescence output. Interestingly, the ON/OF ratio can be enhanced by reducing the distance between the redox active unit and the QD due to a more efficient electronic coupling. Remarkably, by defining a mixed‐valence state, a ternary switch has also been achieved. It is highlighted that the QD surface immobilization is key to realize this switch to avoid aggregation and fluorescence quenching in suspension. Hence, an efficient and versatile novel route to fabricate robust fluorescent redox switches is demonstrated, opening a wide avenue of possibilities to be explored in the field of sensing and information storage.

Voltage-Controlled ON-OFF-Switching of Magnetoresistance in FeOx/Fe/Au Aerogel Networks.

Voltage control of magnetoresistance (MR) in nanoscale three-dimensional (3D) geometries is interesting from a fundamental point of view and a promising route toward novel sensors and energy-efficient computing schemes. Magneto-ionic mechanisms are favorable for low-voltage control of magnetism and room-temperature operation, but magneto-ionic control of MR has been studied only for planar geometries so far. We synthesize a 3D nanomaterial with magneto-ionic functionality by electrodepositing an iron hydroxide/iron coating on a porous nanoscale gold network (aerogel). To enable maximum magneto-ionic ON-OFF-switching, the thickness of the coating is adjusted to a few nanometers by a self-terminating electrodeposition process. In situ magnetotransport measurements during electrolytic gating of these nanostructures reveal large reversible changes in MR, including ON-OFF-switching of MR, with a small applied voltage difference (1.72 V). This effect is related to the electrochemical switching between a ferromagnetic iron shell/gold core nanostructure (negative MR at the reduction voltage) and an iron oxide shell/gold core nanostructure (negligible MR at the oxidation voltage).

Developing an Electrochemically Reversible Switch for Modulating the Optical Signal of Gold Nanoparticles.

Gold nanoparticles (AuNPs) possess remarkable optical properties and electrical conductivity, making them highly relevant in various fields such as medical diagnoses, biological imaging, and electronic sensors. However, the existing methods for modulating the optical properties of AuNPs are often under limitations such as a high cost, the complexity of detection, a narrow range of application settings, and irreversibility. In this study, we propose a novel approach to address these challenges by constructing a reversible electrochemical switch. The switch (ITO-OMAD) involves covalently linking nitroxide radicals and AuNPs (AuNPs-NO•), followed by tethering this nanocomposite to a siloxane-derived indium tin oxide (ITO) electrode. By simply electrochemically oxidizing/reducing the nitroxide units, one is able to reversibly modulate the optical properties of AuNPs at will. The surface morphology and structure of the as-prepared ITO-OMAD electrode were characterized through scanning electron microscopy (SEM) and cyclic voltammetry (CV). SEM imaging confirmed the successful anchoring of AuNPs on the ITO electrode. Electrochemical tests performed in the three-electrode system demonstrated that the local surface plasmon resonance (LSPR) of AuNPs can be reversibly regulated by alternatively imposing ± 0.5V (vs. Ag/AgCl) to the modified electrode. The development of this electrochemical switch presents a novel approach to effectively control the optical properties of AuNPs. The further exploration and utilization of this reversible electrochemical switch could significantly enhance the versatility and practicality of AuNPs in numerous applications.

Quantifying Electrochemical Driving Force for Exsolution in Perovskite Oxides by Designing Graded Oxygen Chemical Potential.

Metal nanoparticles exsolved and anchored at the parent perovskite oxide surfaces can greatly enhance the activity and antisintering stability for high-temperature (electro-) chemical catalytic reactions. While exsolution of nanoparticles triggered by using conventional high-temperature thermal reduction suffers from slow kinetics, using an electrochemical driving force can promote the exsolution rate. However, a quantitative correlation between the applied electrochemical driving force and the spatial density of exsolved nanoparticles remains unknown. In this work, we use a specially designed electrochemical device to induce a spatially graded voltage in a La0.43Ca0.37Ti0.94Ni0.06O3-δ electrode, in order to systematically investigate the effect of electrochemical switching on exsolution. With increasing driving force, which leads to decreasing oxygen chemical potential, the density of nanoparticles was observed to increase dramatically, while the average particle size remained roughly constant. We further identified oxygen vacancy pairs or clusters as the preferential nucleation sites for exsolution. Our work provided a high-throughput platform for the systematic study of exsolution of perovskite oxides targeted for fuel electrode materials with improved electrocatalytic performance and stability.

Impact of Side Chain Extension on the Morphology and Electrochemistry of Phosphonated Poly(Ethylenedioxythiophene) Derivatives

AbstractOne factor with great bearing on the electrochemical performance of conjugated polymers is the film morphology. A balance between crystalline and amorphous domains needs to be achieved for the polymer to have an optimal ionic‐electronic conductance. Herein, the morphological and electrochemical properties of poly(ethylenedioxythiophene) polymers functionalized with phosphonate groups separated by methylene and butylene alkyl spacers from the backbone are compared. Extending the spacer from methylene to butylene increases structural ordering in the solid state as revealed by grazing‐incidence wide‐angle X‐ray scattering. However, the ordered domains are only short range, suggestive of a paracrystalline morphology in which ordered regions are separated by amorphous regions. This has a negative impact on the intermolecular charge transport. The longer spacer appears to have impeded the uptake of hydrated counterions, seen by the increase in the ionization potential and energy requirement for electrochemical switching, as well as the decrease in the volumetric capacitance. These results elucidate the advantages of having the phosphonate pendant group close to the backbone, separated only by a methylene spacer. This synthetic design likely facilitates hydrated counterions to accumulate around the polar phosphonate groups, close to the doped backbone where they can easily compensate the charge carriers formed upon oxidation.

Electrochemical fluorescence switching of enhanced green fluorescent protein

Switchable fluorescent proteins, for which fluorescence can be switched ON and OFF, are widely used for molecule tracking and super resolution imaging. However, the robust use of the switchable fluorescent proteins is still limited as either the switching is not repeatable, or such switching requires irradiation with coupled lasers of different wavelengths. Herein, we report an electrochemical approach to reversible fluorescence switching for enhanced green fluorescent proteins (EGFP) on indium tin oxide coated glass. Our results demonstrate that negative and positive electrochemical potentials can efficiently switch the fluorescent proteins between the dim (OFF) and bright (ON) states at the single molecule level. The electrochemical fluorescence switching is fast, reversible, and may be performed up to hundreds of cycles before photobleaching occurs. These findings highlight that this method of electrochemical fluorescence switching can be incorporated into advanced fluorescence microscopy.

Solution-based carbon quantum dots as electrochemical “on–off” switch in aqueous medium: Engineering of a sustainable green sensor and its computational investigation

It is crucial to establish sensitive electroanalysis of pollutants in water environments, but this is difficult due to their redox inertness and uncertain detection methods. We herein report an electrochemical switch ‘on–off sensor for the selective detection of Hg(II) and amoxicillin (AMX) based on a switch platform system. Our design used a carbon quantum dot (CQD)-based sensing probe (SP) to intensify the electrochemical signal due to its excellent conductivity. The “switch-on” state was attained by introducing the Hg(II) ions and sensing probe (SP) onto the electrode surface to facilitate electron transfer. The modified electrode signifies an excellent electrocatalytic activity of Hg (II), giving sharp anodic and cathodic peaks at 0.53 and 0.42 (V vs. SCE), respectively. Upon addition of AMX, it cleaves the SP into fragments from the sensing interface, hindering the electrochemical signal to create a “switch-off” state. As expected, the SP displayed a desirable linear response range from 0.0 to 100 nM and the detection limit down to 15.0 nM. Density functional theory (DFT) calculations confirm that the binding energy of the AMX with the Hg(II) ion is greater than that of SP and Hg(II). Moreover, the probe showed excellent stability and reproducibility with Hg(II) selectively; thus, it confines great scope for application in environmental water sciences. Further, the switch “on–off” sensing behavior of SP providing two chemical inputs (Hg (II) and AMX) helps to set up an INHIBIT logic gate. A series of experiments, including DFT and electrochemistry, demonstrate the detection mechanism and enhanced electrochemical sensitivity. This sustainable engineering approach creates a perfect sensor using a carbon quantum dots-based sensing probe from waste paper.