A systematic study of electrochemically roughened (ECR) thin film platinum (Pt) microelectrodes for glutamate, GLU (a major excitatory neurotransmitter) detection is presented. Scanning electron microscopy, energy dispersive spectroscopy, surface profilometry, electrochemical impedance spectroscopy and amperometry techniques were applied to investigate the effect of high-frequency electrical pulses on Pt microelectrode roughness, electroactive area, charge transfer resistance, and sensitivity and selectivity to hydrogen peroxide, a by-product of enzymatic biosensors and GLU. An increase in the mean surface roughness from 9.0 ± 0.5 to 116.3 ± 7.4 nm (n = 3) was observed which resulted in a 55 ± 2% (n = 3) increase in the electroactive area. An ECR microelectrode treated at +1.4 V and coated with a selective coating produced a GLU selectivity value of 342 ± 34 (n = 3) vs ascorbic acid and the highest GLU sensitivity of 642 ± 45 nA
Electrochemical characterization of the stimuli-response of surface-immobilized elastin-like polymers
Elastin-like polymers (ELPs) are frequently used in a variety of bioengineering applications because of their stimuli-responsive properties. Above their transition temperature, ELPs will adopt different structures that promote intra- and intermolecular hydrophobic contacts to minimize unfavorable interactions with an aqueous environment. We electrochemically characterize the stimuli-responsive behavior of surface-immobilized ELPs corresponding to two proposed states: extended and collapsed. In the extended state the ELPs are more solvated. In the collapsed state, triggered by introducing an environmental stimulus, non-polar intramolecular contacts within ELPs are favored, resulting in quantifiable morphological changes on the surface characterized using electrochemical impedance spectroscopy (EIS). Charge transfer resistance, a component of impedance, was shown to increase after exposing an ELP modified electrode to a high salt concentration environment (3.0 M NaCl). An increase in charge transfer resistance indicates an increase in the insulating layer on the electrode surface consistent with the proposed mechanism of collapse, as the ELPs have undergone morphological changes to hinder the kinetics of the redox couple exchange. Further characterization of the surface-immobilized ELPs showed a reproducible surface modification, as well as reversibility and tunability of the stimuli-response.
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- NSF-PAR ID:
- 10124973
- Date Published:
- Journal Name:
- Soft Matter
- ISSN:
- 1744-683X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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μ M−1cm−2(n = 3) when compared to other surface-treated Pt microelectrodes reported in the literature. An impedance model was created to elucidate the microstructural and electrochemical property changes to the ECR microelectrodes. The ECR surface comprises of uniformly distributed homogenous pores with very low impedance, which is ∼6-times lower when compared to a methanol cleaned electrode. The model could lay a foundation for the rational designing of biosensors for enhanced neurotransmitter detection. -
Increasing fossil fuel demands and growing concerns of global climate change have stimulated interest in the development of electrocatalysts to produce H 2 as an alternative zero-emission fuel from the electrolysis of water via hydrogen evolution reaction (HER). Precious or non-precious catalysts are typically loaded on high surface area carbon materials, and these supports play a critical role in both thermodynamics and kinetics of the HER. In this paper, we evaluate the electrocatalytic activity of a molecular hydrogen evolving catalyst, diacetyl-bis(4-methyl)-3-thiosemicarbazone Ni( ii ) (Ni-ATSM), on three different carbon surfaces: glassy carbon, carbon paste and pencil graphite. The overpotential for each modified electrode was benchmarked at a current density of −10 mA cm −2 . Carbon paste electrodes showed highest overpotentials (495 mV) compared to the other electrode surfaces. Polished pencil and glassy carbon modified electrodes performed similarly ( η = 395 mV for GCE and η = 400 mV for pencil). Pencil electrodes etched in acetone overnight prior to Ni-ATSM deposition produced lowest overpotentials ( η = 354 mV). Etching results in an increase in electroactive surface area and substantial decrease in the charge transfer resistance of the graphitic interface from 275 Ω to 50 Ω, verified using electrochemical impedance spectroscopy (EIS). Our studies demonstrate pencil graphite may serve as versatile, disposable, cost effective, and reproducible electrode surface for the evaluation of heterogeneous HER catalysts. Moreover, pencils can be easily cut with table saw to generate new surface for easy characterization of the surface such as electrochemistry, imaging and spectroscopy.more » « less
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Zero-mode waveguides (ZMW) have the potential to be powerful confinement tools for studying electron transfer dynamics at single molecule occupancy conditions. Flavin mononucleotide contains an isoalloxazine chromophore, which is fluorescent in the oxidized state (FMN) while the reduced state (FMNH 2 ) exhibits dramatically lower light emission, i.e. a dark-state. This allows fluorescence emission to report the redox state of single FMN molecules, an observation that has been used previously to study single electron transfer events in surface-immobilized flavins and flavoenzymes, e.g. sarcosine oxidase, by direct wide-field imaging of ZMW arrays. Single molecule electron transfer dynamics have now been extended to the study of freely diffusing molecules using fluorescence measurements of Au ZMWs under single occupancy conditions. The Au in the ZMW serves both as an optical cladding layer and as the working electrode for potential control, thereby accessing single molecule electron transfer dynamics at μM concentrations. Consistent with expectations, the probability of observing single reduced molecules increases as the potential is scanned negative, E appl < E eq , and the probability of observing emitting oxidized molecules increases at E appl > E eq . Different single molecules exhibit different electron transfer properties as reflected in the position of E eq and the distribution of E eq among a population of FMN molecules. Two types of actively-controlled electroluminescence experiments were used: chronofluorometry experiments, in which the potential is alternately stepped between oxidizing and reducing potentials, and cyclic potential sweep fluorescence experiments, analogous to cyclic voltammetry, these latter experiments exhibiting a dramatic scan rate dependence with the slowest scan rates showing distinct intermediate states that are stable over a range of potentials. These states are assigned to flavosemiquinone species that are stabilized in the special environment of the ZMW nanopore.more » « less
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All-solid-state batteries (ASSBs) have garnered increasing attention due to the enhanced safety, featuring nonflammable solid electrolytes as well as the potential to achieve high energy density. 1 The advancement of the ASSBs is expected to provide, arguably, the most straightforward path towards practical, high-energy, and rechargeable batteries based on metallic anodes. 1 However, the sluggish ion transmission at the cathode-electrolyte (solid/solid) interface would result in the high resistant at the contact and limit the practical implementation of these all solid-state materials in real world batteries. 2 Several methods were suggested to enhance the kinetic condition of the ion migration between the cathode and the solid electrolyte (SE). 3 A composite strategy that mixes active materials and SEs for the cathode is a general way to decrease the ion transmission barrier at the cathode-electrolyte interface. 3 The active material concentration in the cathode is reduced as much as the SE portion increases by which the energy density of the ASSB is restricted. In addition, the mixing approach generally accompanies lattice mismatches between the cathode active materials and the SE, thus providing only limited improvements, which is imputed by random contacts between the cathode active materials and the SE during the mixing process. Implementing high-pressure for the electrode and electrolyte of ASSB in the assembling process has been verified is a but effective way to boost the ion transmission ability between the cathode active materials and the SE by decreasing the grain boundary impedance. Whereas the short-circuit of the battery would be induced by the mechanical deformation of the electrolyte under high pressure. 4 Herein, we demonstrate a novel way to address the ion transmission problem at the cathode-electrolyte interface in ASSBs. Starting from the cathode configuration, the finite element method (FEM) was employed to evaluate the current concentration and the distribution of the space charge layer at the cathode-electrolyte interface. Hierarchical three-dimensional (HTD) structures are found to have a higher Li + transfer number (t Li+ ), fewer free anions, and the weaker space-charge layer at the cathode-electrolyte interface in the resulting FEM simulation. To take advantage of the HTD structure, stereolithography is adopted as a manufacturing technique and single-crystalline Ni-rich (SCN) materials are selected as the active materials. Next, the manufactured HTD cathode is sintered at 600 °C in an N 2 atmosphere for the carbonization of the resin, which induces sufficient electronic conductivity for the cathode. Then, the gel-like Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP) precursor is synthesized and filled into the voids of the HTD structure cathode sufficiently. And the filled HTD structure cathodes are sintered at 900 °C to achieve the crystallization of the LATP gel. Scanning transmission electron microscopy (STEM) is used to unveil the morphology of the cathode-electrolyte interface between the sintered HTD cathode and the in-situ generated electrolyte (LATP). A transient phase has been found generated at the interface and matched with both lattices of the SCN and the SE, accelerating the transmission of the Li-ions, which is further verified by density functional theory calculations. In addition, Electron Energy Loss Spectroscopy demonstrates the preserved interface between HTD cathode and SEs. Atomic force microscopy is employed to measure the potential image of the cross-sectional interface by the peak force tapping mode. The average potential of modified samples is lower than the sample that mix SCN and SEs simply in the 2D planar structure, which confirms a weakened space charge layer by the enhanced contact capability as well as the ion transmission ability. To see if the demonstrated method is universally applicable, LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is selected as the cathode active material and manufactured in the same way as the SCN. The HTD cathode based on NCM811 exhibits higher electrochemical performance compared with the reference sample based on the 2D planar mixing-type cathode. We believe such a demonstrated universal strategy provides a new guideline to engineer the cathode/electrolyte interface by revolutionizing electrode structures that can be applicable to all-solid-state batteries. Figure 1. Schematic of comparing of traditional 2D planar cathode and HTD cathode in ASSB Tikekar, M. D. , et al. , Nature Energy (2016) 1 (9), 16114 Banerjee, A. , et al. , Chem Rev (2020) 120 (14), 6878 Chen, R. , et al. , Chem Rev (2020) 120 (14), 6820 Cheng, X. , et al. , Advanced Energy Materials (2018) 8 (7) Figure 1more » « less
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Abstract Two-dimensional (2D) ternary materials recently generated interest in optoelectronics and energy-related applications, alongside their binary counterparts. To date, only a few naturally occurring layered 2D ternary materials have been explored. The plethora of benefits owed to reduced dimensionality prompted exploration of expanding non-layered ternary chalcogenides into the 2D realm. This work presents a templating method that uses 2D transition metal dichalcogenides as initiators to be converted into the corresponding ternary chalcogenide upon addition of copper, via a solution-phase synthesis, conducted in high boiling point solvents. The process starts with preparation of VSe2nanosheets, which are next converted into Cu3VSe4sulvanite nanosheets (NSs) which retain the 2D geometry while presenting an X-ray diffraction pattern identical with the one for the bulk Cu3VSe4. Both the scanning electron microscopy and transmission microscopy electron microscopy show the presence of quasi-2D morphology. Recent studies of the sulfur-containing sulvanite Cu3VS4highlight the presence of an intermediate bandgap, associated with enhanced photovoltaic (PV) performance. The Cu3VSe4nanosheets reported herein exhibit multiple UV–Vis absorption peaks, related to the intermediate bandgaps similar to Cu3VS4and Cu3VSe4nanocrystals. To test the potential of Cu3VSe4NSs as an absorber for solar photovoltaic devices, Cu3VSe4NSs thin-films deposited on FTO were subjected to photoelectrochemical testing, showing p-type behavior and stable photocurrents of up to ~ 0.036 mA/cm2. The photocurrent shows a ninefold increase in comparison to reported performance of Cu3VSe4nanocrystals. This proves that quasi-2D sulvanite nanosheets are amenable to thin-film deposition and could show superior PV performance in comparison to nanocrystal thin-films. The obtained electrical impedance spectroscopy signal of the Cu3VSe4 NSs-FTO based electrochemical cell fits an equivalent circuit with the circuit elements of solution resistance (Rs), charge-transfer resistance (Rct), double-layer capacitance (Cdl), and Warburg impedance (W). The estimated charge transfer resistance value of 300 Ω cm2obtained from the Nyquist plot provides an insight into the rate of charge transfer on the electrode/electrolyte interface.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9SM01681C
