Heterogeneous Electron Transfer Research Articles

The Electrostatic Stimulation of Adsorbed Carbon Monoxide Oxidation on Pt in Aqueous Acidic Electrolytes

The oxidation of adsorbed carbon monoxide on Pt electrodes, CO(ads)|Pt, in aqueous electrolytes ranks among the most studied reactions in electrocatalysis both from theoretical[1]and experimental viewpoints.[2][3] Much of the interest in this electron transfer process stems from the role CO(ads) plays as an impurity that affects adversely the operation of H2|O2 fuel cells. Consensus appears to have been reached regarding the role of adsorbed hydroxyl, OH.(ads) in controlling the activation and ultimate oxidation of CO(ads). The present contribution illustrates the use of electrochemical stimulation techniques developed in our laboratory[4] to explore new aspects of this process not as yet unveiled by the use of more conventional methods. As described in our earlier publications,[4,5] electrode stimulation refers to changes in the rates of heterogeneous electron transfer processes involving adsorbed species induced by modifications in the electrostatic potential in the solution immediately adjacent to the electrode generated by the passage of current between an electrode placed very close to the working electrode, WE, polarized at constant potential, and a second electrode far away from it. The electrochemical cell used for these experiments consisted of a glass tube covered at each end with custom-made Teflon caps and, thus, similar in design to that described by Qi et al.[4] Experiments were performed in Ar-purged 0.1 M H2SO4 involving CO adsorbed at saturation coverages on polycrystalline Pt, polarized at EWE = 0.8 V, a potential very close to the onset of CO(ads) oxidation with a Au disk electrode placed directly above it working as a stimulating electrode, SE, i.e. face to face configuration. Shown in Fig. 1 are plots of the current flowing through the SE (red), iSE and iWE (black) (see Left Panel) and their expanded views during stimulation (Middle Panel) and CO full oxidation (Right Panel), respectively. As shown in the middle panel in this figure. the passage of a negative iSE, elicits a positive iWE ascribed to CO oxidation, which persists even when iSE turns positive, until the end of the stimulation process (see Right Panel), which takes several seconds. In brief, a single stimulation lasting 140 ms can trigger the full oxidation of the entire adsorbed CO layer in CO|Pt over a subsequent period of ca. 4 s. The most likely explanation for this unique effect may be found in the formation of adsorbed OH. on sites previously covered with CO, as the CV of bare Pt would strongly suggest, which will promote the subsequent oxidation of CO(ads), a process that will propagate through the entire Pt surface. Further support for this mechanism was provided by an experiment in which the WE potential was stepped down to 0.4 V immediately after the stimulation was applied, which stopped virtually instantaneously the further oxidation of CO(ads). Experiments are now in progress to image the surface of the CO|Pt electrode during and after the stimulation to monitor in real time the rates of propagation and to provide a more details theoretical model to account for this phenomenon. References 1 Gao, W.; Mueller, J.E.; Jiang, Q.; Jacob, T. Angew. Chem. Int. Ed. 2012, 51, 9448 –94522 Scott, S.B.; Kibsgaarda, J.; Vesborga, P.C.K.; Chorkendorff, I. Electrochim. Acta 2021, 374, 1378423 Scott, S.B.; Kibsgaarda, J.; Vesborga, P.C.K.; Chorkendorff, I. Electrochim. Acta 2021, 374, 1378444 Han, Q.; Georgescu, N. S.; Gibbons, J.; Scherson, D. Electrochim. Acta 2019, 325, 1349575 Heer, A.S.; Mantelli, H; Han, Q.; Georgescu, N. S.; Scherson, D. in preparation. Acknowledgement Support for this work provided by NSF, CHE-1808592.Fig. 1. Plots of iWE and iSE recorded for EWE = 0.8 V prior, during and following WE stimulation (see text for details) (Left Panel). The middle and right panels show expanded views of the data in the left panel during stimulation and CO full oxidation, respectively. Figure 1

Visualizing Reaction Distributions for Materials Validation and Failure Analysis in Li-Ion Batteries

A real-time, high-throughput visualization technique for heterogeneity in lithium-ion battery (LIB) electrodes is necessary to understand battery performance on a mechanistic level. Our group, along with others, has seen that battery performance is governed by short range (<20 um) electron transfer between the active material and carbon binder domain (CBD) within electrodes [1]–[3]. Available imaging techniques for visualizing the electronic connectivity of LIB electrodes are limited to nanoscale, single particle resolutions using sophisticated synchrotron X-ray or electron microscopy [4]–[6]. Optical microscopy offers the correct spatial resolution for visualizing the submicron connection of active particles to CBD, but is limited by colorimetry of electrode materials- with graphite being the exception due to its visible color change during lithiation [7]. There is a rapidly growing body of research interested in studying the ionic diffusion pathways of Li-ion using operando optical microscopy, however none currently exist for studying the submicron electronic connectivity through a facile, operando approach- especially under a industrially applicable lens [8]. To the best of our knowledge, this study presents the first spatially- and time- resolved technique for visualizing the electronic connectivity of commercial LIB electrodes using operando electrochemical fluorescent microscopy (EFM). This technique relies on the principle of electrofluorochromism, which we use to our advantage for a simple electrochemical system involving heterogeneous electron transfer. This allows us to use fluorescence as a real-time tracker for electronic heterogeneity, where electronic ‘dead-zones’ present as non-fluorescent regions in 2D images.Using our technique, we visualize commonly used commercial LIB electrodes (carbon content 1-4%, regimented processing), including NMC (LiNixMnyCo1-x-yO2), LFP (LiFePO4), and LCO (LiCoO2) against formulaically similar in-house made LIB electrodes (< 3.5% carbon content) as a proof of concept. We first validate the efficacy of this technique by testing commercial NMC, with a flaked off piece of active material, to show that areas of electronic discontinuities can in fact be represented by non-fluorescence (Fig.1.) We also find that when compared to commercial electrodes, those which are fabricated in house reveal isolated active particles, agglomerated carbon islands, and dead zones, undiscernible by brightfield imaging (Fig. 2.) Global feature extraction is performed on post-processed images to quantify electrode topology and evaluate electronic connectivity of active particles of battery electrodes, as well as heterogeneous mapping to determine the heterogeneity index of electrodes imaged. Testing our technique on low- and high- performing electrodes from an established library of coin-cell data allows for a straightforward way of correlating performance metrics to heterogeneity features. This quick (<1hr), reproducible visualization technique is general enough to be used to study the electronic connectivity of emerging new battery electrodes, as well as verify commercially available ones. Using this approach to verify LIB electrodes prior to assembly could save months to years of battery testing by being used as an alternative to lengthy full cell testing.[1] S. L. Morelly, N. J. Alvarez, and M. H. Tang, “Short-range contacts govern the performance of industry-relevant battery cathodes,” Journal of Power Sources, vol. 387, pp. 49–56, May 2018, doi: 10.1016/j.jpowsour.2018.03.039.[2] R. M. Saraka, S. L. Morelly, M. H. Tang, and N. J. Alvarez, “Correlating Processing Conditions to Short- and Long-Range Order in Coating and Drying Lithium-Ion Batteries,” ACS Appl. Energy Mater., vol. 3, no. 12, pp. 11681–11689, Dec. 2020, doi: 10.1021/acsaem.0c01305.[3] J. Entwistle, R. Ge, K. Pardikar, R. Smith, and D. Cumming, “Carbon binder domain networks and electrical conductivity in lithium-ion battery electrodes: A critical review,” Renewable and Sustainable Energy Reviews, vol. 166, p. 112624, Sep. 2022, doi: 10.1016/j.rser.2022.112624.[4] S. Li et al., “Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides,” Nat Commun, vol. 11, no. 1, Art. no. 1, Sep. 2020, doi: 10.1038/s41467-020-18278-y.[5] P.-C. Tsai et al., “Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries,” Energy Environ. Sci., vol. 11, no. 4, pp. 860–871, Apr. 2018, doi: 10.1039/C8EE00001H.[6] A. Singer et al., “Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging,” Nat Energy, vol. 3, no. 8, Art. no. 8, Aug. 2018, doi: 10.1038/s41560-018-0184-2.[7] Y. Yamagishi, H. Morita, Y. Nomura, and E. Igaki, “Visualizing Lithiation of Graphite Composite Anodes in All-Solid-State Batteries Using Operando Time-of-Flight Secondary Ion Mass Spectrometry,” J. Phys. Chem. Lett., vol. 12, no. 19, pp. 4623–4627, May 2021, doi: 10.1021/acs.jpclett.1c01089.[8] A. J. Merryweather, C. Schnedermann, Q. Jacquet, C. P. Grey, and A. Rao, “Operando optical tracking of single-particle ion dynamics in batteries,” Nature, vol. 594, no. 7864, Art. no. 7864, Jun. 2021, doi: 10.1038/s41586-021-03584-2. Figure 1

Operando Electrochemical Fluorescent Microscopy to Predict Li-Ion Battery Performance

A real-time, high-throughput visualization technique for heterogeneity in lithium-ion battery (LIB) electrodes is necessary to understand battery performance on a mechanistic level. Our group, along with others, has seen that battery performance is governed by short range (<20 um) electron transfer between the active material and carbon binder domain (CBD) in electrodes [1]–[3]. Available imaging techniques for visualizing the electronic connectivity of LIB electrodes are limited to nanoscale, single particle resolutions using sophisticated synchrotron X-ray or electron microscopy [4]–[6]. Optical microscopy offers the correct spatial resolution for visualizing the submicron connections of active particles to CBD, but is limited by the colorimetry of electrode materials- with graphite being the exception due to its visible color change during lithiation [7]. There is a rapidly growing body of research interested in studying the ionic diffusion pathways of Li-ion using operando optical microscopy, however none currently exist for studying the submicron electronic connectivity using an operando approach- especially under a industrially applicable lens [8]. To the best of our knowledge, this study presents the first spatially- and time- resolved technique for visualizing the electronic connectivity of commercial LIB electrodes using operando electrochemical fluorescent microscopy (EFM). This technique relies on the principle of electrofluorochromism, which we use to our advantage for a simple electrochemical system involving heterogeneous electron transfer. This allows us to use fluorescence as a real-time tracker for electronic heterogeneity, where electronic ‘dead-zones’ present as non-fluorescent regions in 2D images.Using this technique, we visualize commonly used commercial LIB electrodes (carbon content 1-4%, regimented processing), including NMC (LiNixMnyCo1-x-yO2), LFP (LiFePO4), and LCO (LiCoO2) against formulaically similar in-house made LIB electrodes (< 3.5% carbon content) as a proof of concept. We first validate the efficacy of this technique by testing commercial NMC, with a flaked off piece of active material, to show that areas of electronic discontinuities can in fact be represented by non-fluorescence (Fig.1.) We also find that when compared to commercial electrodes, those which are fabricated in house reveal isolated active particles, agglomerated carbon islands, and dead zones, undiscernible by brightfield imaging (Fig. 2.) Global feature extraction is performed on post-processed images to quantify electrode topology and evaluate electronic connectivity of active particles of battery electrodes, as well as heterogeneous mapping to determine the heterogeneity index of electrodes imaged. Testing our technique on low- and high- performing electrodes from an established library of coin-cell data allows for a straightforward way of correlating performance metrics to heterogeneity features. This quick (<1hr), reproducible visualization technique is general enough to be used to study the electronic connectivity of emerging new battery electrodes, as well as verify commercially available ones. Using this approach to verify LIB electrodes prior to assembly could save months to years of battery testing by being used as an alternative to lengthy full cell testing.[1] S. L. Morelly, N. J. Alvarez, and M. H. Tang, “Short-range contacts govern the performance of industry-relevant battery cathodes,” Journal of Power Sources, vol. 387, pp. 49–56, May 2018, doi: 10.1016/j.jpowsour.2018.03.039.[2] R. M. Saraka, S. L. Morelly, M. H. Tang, and N. J. Alvarez, “Correlating Processing Conditions to Short- and Long-Range Order in Coating and Drying Lithium-Ion Batteries,” ACS Appl. Energy Mater., vol. 3, no. 12, pp. 11681–11689, Dec. 2020, doi: 10.1021/acsaem.0c01305.[3] J. Entwistle, R. Ge, K. Pardikar, R. Smith, and D. Cumming, “Carbon binder domain networks and electrical conductivity in lithium-ion battery electrodes: A critical review,” Renewable and Sustainable Energy Reviews, vol. 166, p. 112624, Sep. 2022, doi: 10.1016/j.rser.2022.112624.[4] S. Li et al., “Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides,” Nat Commun, vol. 11, no. 1, Art. no. 1, Sep. 2020, doi: 10.1038/s41467-020-18278-y.[5] P.-C. Tsai et al., “Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries,” Energy Environ. Sci., vol. 11, no. 4, pp. 860–871, Apr. 2018, doi: 10.1039/C8EE00001H.[6] A. Singer et al., “Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging,” Nat Energy, vol. 3, no. 8, Art. no. 8, Aug. 2018, doi: 10.1038/s41560-018-0184-2.[7] Y. Yamagishi, H. Morita, Y. Nomura, and E. Igaki, “Visualizing Lithiation of Graphite Composite Anodes in All-Solid-State Batteries Using Operando Time-of-Flight Secondary Ion Mass Spectrometry,” J. Phys. Chem. Lett., vol. 12, no. 19, pp. 4623–4627, May 2021, doi: 10.1021/acs.jpclett.1c01089.[8] A. J. Merryweather, C. Schnedermann, Q. Jacquet, C. P. Grey, and A. Rao, “Operando optical tracking of single-particle ion dynamics in batteries,” Nature, vol. 594, no. 7864, Art. no. 7864, Jun. 2021, doi: 10.1038/s41586-021-03584-2. Figure 1

Photoelectrochemistry of Redox-Active Self-Assembled Monolayers Formed on n-Si/Au Nanoparticle Photoelectrodes.

Controlling the chemistry of the electrode-solution interface is critically important for applications in sensing, energy storage, corrosion prevention, molecular electronics, and surface patterning. While numerous methods of chemically modifying electrodes exist, self-assembled monolayers (SAMs) containing redox-active moieties are particularly important because they are easy to prepare, have well-defined interfaces, and can exhibit textbook photoelectrochemistry. Here, we investigate the photoelectrochemistry of redox-active SAMs on semiconductor/metal interfaces, where the SAM is attached to the metal site instead of the semiconductor. n-Si/Au photoelectrodes were fabricated using a benchtop electrodeposition procedure and subsequently modified by immersion in aqueous solutions of (ferrocenyl)hexanethiol and mercaptohexanol. We explored the relevant preparation conditions, finding that after optimization, we were able to obtain canonical cyclic voltammetry for a surface-bound redox molecule that could be turned on and off using light. We then characterized the optimized electrodes under varying illumination intensities, finding that the heterogeneous electron transfer kinetics improved under higher illumination intensities. These results lay the foundation for future studies of semiconductor/metal/molecule interfaces relevant to sensing and electrocatalysis.

Electrochemical Probing of Human Liver Subcellular S9 Fractions for Drug Metabolite Synthesis

Human liver subcellular fractions, including liver microsomes (HLM), liver cytosol fractions, and S9 fractions, are extensively utilized in in vitro assays to predict liver metabolism. The S9 fractions are supernatants of human liver homogenates that contain both microsomes and cytosol, which include most cytochrome P450 (CYP) enzymes and soluble phase II enzymes such as glucuronosyltransferases and sulfotransferases. This study reports on the direct electrochemistry and biocatalytic features of redox-active enzymes in S9 fractions for the first time. We investigated the electrochemical properties of S9 films by immobilizing them onto a high-purity graphite (HPG) electrode and performing cyclic voltammetry under anaerobic (Ar-saturated) and aerobic (O2-saturated) conditions. The heterogeneous electron transfer rate between the S9 film and the HPG electrode was found to be 14 ± 3 s−1, with a formal potential of −0.451 V vs. Ag/AgCl reference electrode, which confirmed the electrochemical activation of the FAD/FMN cofactor containing CYP450-reductase (CPR) as the electron receiver from the electrode. The S9 films have also demonstrated catalytic oxygen reduction under aerobic conditions, identical to HLM films attached to similar electrodes. Additionally, we investigated CYP activity in the S9 biofilm for phase I metabolism using diclofenac hydroxylation as a probe reaction and identified metabolic products using liquid chromatography–mass spectrometry (LC-MS). Investigating the feasibility of utilizing liver S9 fractions in such electrochemical assays offers significant advantages for pharmacological and toxicological evaluations of new drugs in development while providing valuable insights for the development of efficient biosensor and bioreactor platforms.

Electrochemical and Kinetic Analysis of Manganese Electrolytes for Redox Flow Batteries

The hybrid hydrogen-manganese redox flow battery (H2-Mn RFB) is a promising and sustainable electrochemical system for long-duration energy storage. One strong reason is the excellent features of manganese, such as low cost, abundance, environmental friendliness, and relatively high standard potential (+1.51 V). Nevertheless, the electrochemical and kinetic parameters of manganese electrolytes have not been studied in detail for flow batteries. In the present work, the kinetics of the Mn2+/Mn3+ redox species in an electrolyte composed of 1M TiOSO4 and 1M MnSO4 in 3M H2SO4 were studied on carbon paper electrodes. The kinetic analysis of manganese redox species (Mn2+/Mn3+) in the presence of TiO2+ was performed using cyclic voltammetry and electrochemical impedance spectroscopy techniques within the H2-Mn RFB set-up. The results were compared to reference redox species vanadium (VO2+/VO2 +) within H2-V RFB system. The results showed that the heterogeneous electron transfer rate constant (8.6 × 10−7 cm s−1) of manganese is comparable to that of vanadium (4.8 × 10−6 cm s−1), with less than an order of magnitude difference between them.

Boosting electrochemical performance of single-walled carbon nanotube three-dimensional architectures through appropriate selection of organic dispersant

The choice of organic dispersant in the fabrication of 3D carbon nanotube architectures affects their macroscopic properties. Binder-free papers (referred to as buckypapers, BPs) consisting of single-walled nanotubes (SWCNTs) fabricated by vacuum filtration of nanotube suspensions in isopropanol, ethanol, benzoic acid dissolved in ethanol and lemon oil show a work of adhesion of water that varies from 25.7 to 112.2 mJ·m−2. Bulk electrical resistivity also changes significantly from 145 to 1010 mΩ cm. Raman and FTIR spectra of pristine SWCNTs and BPs show evidence of permanent adsorption of organic molecules on SWCNTs. Heterogeneous electron transfer (HET) standard rate constants, k0, for ferro/ferricyanide and hexaammineruthenium(II)/(III) redox probes estimated from cyclic voltammetry measurements on BP electrodes vary from 12.6×10−4cms−1 to 32.7×10−4cms−1 and 12.8×10−4cms−1 to 26.0×10−4cms−1, respectively, depending on the dispersant used. Calculations using the Gerischer-Marcus model show that molecules adsorbed act as electron donors that boost HET kinetics and cause a shift in the reaction half-wave potential. The level of doping of nanotubes depends on the dipole moment of the dispersant molecules and proton affinity. Thus, the electrocatalytic activity of three-dimensional architectures composed of nanotubes can be adjusted by selecting an appropriate dispersant.

The Hydroxylated Carbon Nanotubes as the Hole Oxidation System in Electrocatalysis.

The hydroxylated carbon nanotubes (CNTs-OH), due to their propensity to trap electrons, are considered in many applications. Despite many case studies, the effect of the electronic structure of the CNT-OH electrode on its oxidation properties has not received in-depth analysis. In the present study, we used Fe(CN)63-/4- and Ru(NH3)63+/2+ as redox probes, which differ in charge. The CNT-OH and CNT electrodes used in the cyclic voltammetry were in the form of freestanding films. The concentration of holes in the CNTs-OH, estimated from the upshift of the Raman G-feature, was 2.9×1013 cm-2. The standard rate constant of the heterogeneous electron transfer (HET) between Fe(CN)63-/4- and the CNTs-OH electrode was 25.9×10-4 cm·s-1. The value was more than four times higher than the HET rate on the CNT electrode (ks=6.3×10-4 cm·s-1), which proves excellent boosting of the redox reaction by the holes. The opposite effect was observed for the Ru(NH3)63+/2+ redox couple. While the redox reaction rate constant at the CNT electrode was 1.4×10-4 cm·s-1, there was a significant suppression of the redox reaction at the CNT-OH electrode (ks<0.1×10-4 cm·s-1). Based on the DFT calculations and the Gerischer model, we find that the boosting of the HET from the reduced form of the redox couple to CNT-OH occurs when the reduced forms of the redox couples are negatively charged and the occupied reduced states are aligned with acceptor states of the nanotube electrode.

Nanomolar detection of organic pollutant -tartrazine in food samples using zinc-metal organic framework/carbon nano fiber - composite modified screen-printed electrode

In this study, we achieved a significant breakthrough by applying a binder-free Zn-MOF@CNF composite as a modifier on a screen-printed electrode (SPE) to achieve highly sensitive and selective detection of tartrazine (TRZ). This composite, with its unique rod-like structure for Zn-MOF and a curl thread-like morphology for carbon nanofibers (CNF), demonstrated a remarkable threefold increase in the sensing current of TRZ at a lower anodic oxidation potential (0.92 V) compared to the bare SPE. The Zn-MOF@CNF/SPE also exhibited a reduced charge transfer resistance of 61.9 Ω, elevated electrochemical active surface area of 0.416 cm2, and high heterogeneous electron transfer rate constant (k0) of 9.77×10−5 cm s−1. Furthermore, it displayed a broad linear range from 0.2 μM to 1000 μM with a remarkable sensitivity of 0.136 µAµM−1cm−2 and an impressive detection limit of 54 nM. Ultimately, the developed Zn-MOF@CNF/SPE sensor demonstrated excellent selectivity amidst various structurally similar overlapping species, outstanding repeatability, reproducibility, and stability in TRZ detection. The practical applicability of Zn-MOF@CNF/SPE was validated through 97 – 100.9 % recovery results in food samples such as jelly, ice cream, soft drinks, and candies.

Optimised graphite/carbon black loading of recycled PLA for the production of low-cost conductive filament and its application to the detection of β-estradiol in environmental samples

The production, optimisation, physicochemical, and electroanalytical characterisation of a low-cost electrically conductive additive manufacturing filament made with recycled poly(lactic acid) (rPLA), castor oil, carbon black, and graphite (CB-G/PLA) is reported. Through optimising the carbon black and graphite loading, the best ratio for conductivity, low material cost, and printability was found to be 60% carbon black to 40% graphite. The maximum composition within the rPLA with 10 wt% castor oil was found to be an overall nanocarbon loading of 35 wt% which produced a price of less than £0.01 per electrode whilst still offering excellent low-temperature flexibility and reproducible printing. The additive manufactured electrodes produced from this filament offered excellent electrochemical performance, with a heterogeneous electron (charge) transfer rate constant, k0 calculated to be (2.6 ± 0.1) × 10−3 cm s−1 compared to (0.46 ± 0.03) × 10−3 cm s−1 for the commercial PLA benchmark. The additive manufactured electrodes were applied to the determination of β-estradiol, achieving a sensitivity of 400 nA µM−1, a limit of quantification of 70 nM, and a limit of detection of 21 nM, which compared excellently to other reports in the literature. The system was then applied to the detection of ß-estradiol within four real water samples, including tap, bottled, river, and lake water, where recoveries between 95 and 109% were obtained. Due to the ability to create high-performance filament at a low material cost (£0.06 per gram) and through the use of more sustainable materials such as recycled polymers, bio-based plasticisers, and naturally occurring graphite, additive manufacturing will have a permanent place within the electroanalysis arsenal in the future.Graphical abstract

In Situ and 2D and 3D in Silico Redox Cycling Studies for Design Optimization of Coplanar Arrays of Microband Electrodes in a 70 μm × 100 μm Electroactive Footprint

Optimization of redox-cycling currents was performed by adjusting the height (sidewalls, h), width (w), and length (l) of band electrodes and their spacing (w gap) in coplanar arrays restricted to a small-electroactive window of 70 × 100 μm. These arrays can function in μL-volumes for chemical analysis (e.g., in-vivo dopamine detection using probes). Experiments were conducted with an array of five electrodes (N E = 5), w = 4.3 μm, w gap = 3.7 μm, h = 0.150 μm, and l = 99.2 μm. Reasons for disparities between currents from experiments and approximate equations were determined by high-density mesh simulations and were found to arise from sluggish heterogeneous electron transfer kinetics and diffusion at electrode ends, edges, and heights. Ferricyanide, with its moderately slow kinetics, exhibits redox-cycling currents that fall below predictions by the equations as w gap decreases and diffusional flux outpaces reaction rates. Simulations aid investigations of various array designs, achievable through conventional photolithography, by decreasing w and w gap and increasing N E to fit within the electroactive window. A coplanar array, N E = 58, w = w gap = 0.6 μm, h = 0.150 μm and l = 100 μm, yielded ferricyanide sensitivities of 0.266, 0.259 nA·μM−1, enhancements of 8 × and 9 × over w = w gap = 4 μm, and projected dopamine lower limits of quantitation of 139 nM, 171 nM at generator and collector electrodes, respectively.

Elucidation of Design Criteria for V-based Redox Mediators: Structure-Function Relationships that Dictate Rates of Heterogeneous Electron Transfer.

Redox mediators are attractive solutions for addressing the stringent kinetic stipulations required for efficient energy conversion processes. In this work, we compare the electrochemical properties of four vanadium complexes, namely [V(acac)3], [V6O7(OMe)12], [nBu4N]3[V6O13(TRISNO2)2], and [nBu4N]5[V18O46(NO3)] in non-aqueous solutions on glassy carbon electrodes. The goal of this study is to investigate the electron transfer kinetics and diffusivity of these compounds under identical experimental conditions to develop an understanding of structure-function relationships that dictate the physicochemical properties of vanadium oxide assemblies. Complex selection was dictated by two criteria - (1) nuclearity of the transition metal complexes (2) distribution of electron density in the native electronic configuration. Our analyses establish that electronic communication between metal centers significantly impacts charge transfer kinetics of these vanadium-based compounds.

Clarifying sequential electron-transfer steps in single-nanoparticle electrochemical process for identifying the intrinsic activity of electrocatalyst

Single-nanoparticle collision electrochemistry (SNCE) is an effective method for determining the intrinsic activity of electrocatalysts at the single-nanoparticle (NP) level. Despite fruitful advancements in the SNCE field, determining a quantitative relationship between the NP structure and its activity has remained difficult because of an unclear understanding of SNCE. In this study, we successfully uncovered the essential roles of the sequential electron-transfer steps in the SNCE system in regulating the apparent electrocatalytic activity of single NPs. By monitoring the oxygen reduction reaction of individual Pt NPs, significantly distinct apparent activities were observed at different electrodes owing to the rate-determining step-controlled electron transfer process. Furthermore, a new theoretical model is proposed for treating the electrochemical current, which involves NP-electrode electron transfer, heterogeneous electron transfer, and mass transfer in solution as sequential steps in the SNCE system. The combination of theoretical simulations and high-resolution electrochemical measurements allows for the corresponding parameters (contact resistance, heterogeneous kinetic constants, and adsorption possibility) of sequential electron-transfer steps to be quantified, resulting in the identification of a rate-determining step for improving the intrinsic activity of electrocatalysts. This work provides a clear picture for determining the intrinsic activity of single NPs in SNCE measurements and introduces a new conceptual route for the quantification of structure-activity relationships, which ultimately guide the rational design and optimization of electrocatalytic nanomaterials.

Benchmarking Trisaminocyclopropeniums as Mediators for Anodic Oxidation Reactions.

This report benchmarks a tris(amino)cyclopropenium (TAC) salt as an electron-transfer mediator for anodic oxidation reactions in comparison to two known mediators: a triarylamine and a triarylimidazole derivative. The three mediators have redox potentials, diffusion coefficients, and heterogeneous electron transfer rates similar to those of glassy carbon electrodes in acetonitrile/KPF6. However, they differ significantly in their performance in two electro-organic reactions: anodic fluorination of a dithiane and anodic oxidation of 4-methoxybenzyl alcohol. These differences are rationalized based on variable stability in the presence of reaction components (e.g., NEt3·3HF, lutidine, and Cs2CO3) as well as very different rates of electron transfer with the organic substrate. Overall, this work highlights the advantages and disadvantages of each mediator and provides a foundation for expanding the applications of TACs in electro-organic synthesis moving forward.

Novel Ce(OH)CO3/carbon nanotubes hybrid material towards a highly sensitive electrochemical dopamine determination in real urine samples

Cerium hydroxycarbonate and multiwalled carbon nanotubes (Ce(OH)CO3/CNT), drop-casted onto a glassy carbon (GC) electrode and electrochemically treated (tCe(OH)CO3/CNT) has been obtained as a new hybrid material. tCe(OH)CO3/CNT was characterized through SEM, FT-IR, UV–Vis, and electrochemical techniques such as cyclic voltammetry (CV) with different redox couples as Fe2+/3+, Fe(CN)63-/4− or Ru(NH3)62+/3+and electrochemical impedance spectroscopy (EIS) measurements with Fe(CN)63-/4−. The charge transfer resistance (RCT) value of tCe(OH)CO3/CNT was up to two orders of magnitude lower than the RCT of bare GC electrodes and these results were confirmed by the effective heterogeneous electron transfer rate constant values (k°eff, 2.4 10−3 vs 7.0 10−4, respectively). The calibration curve of DA exhibits a linear response within the range of 0.1 and 70 μmol L−1 with a correlation coefficient (R2) of 0.987 (n = 3) and a limit of detection of 0.003 μmol L−1. Inorganic and organic interferents do not alter significatively the selectivity. The electrochemical treatment of Ce(OH)CO3 and CNT generates a modified electrode which successfully combines the selectivity of Ce towards catechol with the high conductivity of CNT presenting an ideal performance for the electrochemical DA determination in 5 real urine samples (1.94 μmol L−1 in a 1:20 dilution) using differential pulse voltammetry (DPV) with an RSD < 6.1 %.

Efficient Electrocatalytic H2 Production by Immobilized Co(III)‐myoglobin

AbstractThe thermodynamics and kinetics of heterogeneous electron transfer (ET) for Co‐substituted horse myoglobin (Co−Mb) and its derivatives with ammonia and imidazole as heme axial ligands were studied with cyclic voltammetry on a pyrolytic graphite electrode along with their ability to mediate the electro‐catalytic production of H2. All the proteins experience a non‐diffusive electrochemical regime as electrode‐bound species. The adsorbed Co−Mb construct carries out the electro‐catalytic reduction of water protons to H2 with a good efficiency under anaerobic conditions thus yielding a simple and tunable system for H2 production. Replacement of H2O as Co axial ligand by ammonia and imidazole significantly lowers the catalytic currents for H3O+/H2O reduction to H2. The E°’ values of the Co(III)/Co(II) redox couple for all species are mainly determined by the enthalpic contribution. Differences were found in the kinetics of ET for the different protein adducts due to changes in the activation enthalpies. However, all species share the same distance of about 14 Å from the electrode surface to the Co(III)/Co(II) center determined using the Marcus model, consistent with a non‐denaturing adsorption of the protein.

Fe Single-Atom Carbon Dots Nanozyme Collaborated with Nucleic Acid Exonuclease III-Driven DNA Walker Cascade Amplification Strategy for Circulating Tumor DNA Detection.

Circulating tumor DNA (ctDNA), as a next-generation tumor marker, enables early screening and monitoring of cancer through noninvasive testing. Exploring the development of new methods for ctDNA detection is an intriguing study. In this work, a unique electrochemical biosensor for the ctDNA detector was constructed in the first utilizing Fe single-atom nanozymes-carbon dots (SA Fe-CDs) as a signaling carrier in collaboration with a DNA walker cascade amplification strategy triggered by nucleic acid exonuclease III (Exo III). The electrochemical active surface area of AuNPs/rGO modified onto a glassy carbon electrode (AuNPs/rGO/GCE) was about 1.43 times that of a bare electrode (bare GCE), with good electrical conductivity alongside a high heterogeneous electron transfer rate (5.81 × 10-3 cm s-1), that is, as well as the ability to load more molecules. Sequentially, the DNA walker cascade amplification strategy driven by Exo III effectively converted the target ctDNA into an amplified biosignal, ensuring the sensitivity and specificity of ctDNA. Ultimately, the electrochemical signal was further amplified by introducing SA Fe-CDs nanozymes, which could serve as catalysts for 3,3',5,5'-tetramethylbenzidine (TMB) oxidation with facile responding (Vmax = 0.854 × 10-6 M s-1) and robust annexation (Km = 0.0069 mM). The integration of the triple signal amplification approach achieved detection limits as low as 1.26 aM (S/N = 3) for a linearity spanning from 5 aM to 50 nM. In this regard, our proposal for a biosensor with exceptional assay properties in complicated serum environments had great potential for early and timely diagnosis of cancer.

Microbiologically influenced corrosion can cause a dental implant rejection

In the present study, we apply electrochemical and molecular biology approaches to establish whether microbiologically influenced corrosion (MIC) may be the reason for dental implant rejection. Titanium-based implants have been incubated in vitro in Ringer/glucose solution in the presence and absence of a salivary microbiota and the change in their corrosion potential and current density was monitored over time by potentiodynamic polarization. The charge transfers processes occurring on the Ti-based implant surface during the initial bacterial adhesion and after biofilm formation were analyzed by electrochemical impedance spectroscopy. The components of the equivalent electrical circuit as well as the heterogeneous electron transfer rate constants were estimated. In parallel, bacterial species from the salivary microbiota have been identified by sequencing of the 16S ribosomal amplicon method, and their contribution to the corrosion processes of dental implants was verified and compared to that of native saliva in vitro. The scanning electron microscopy observation and energy dispersive spectroscopy analysis of the implant surface after long-term exposure to a bacterial-containing environment revealed more detailed features of the occurring corrosion processes.

Efficacy of films of uncapped gold nanoparticle as electrodes for direct electron transfer to redox proteins

Electrochemical manipulation of enzymes is expected to enable the rapid detection of marker molecules and the efficient production of valuable materials. We have fabricated an Au nanoparticle (AuNP) thin film electrode in our previous study, which enables more enhanced heterogeneous electron transfer reactions than a conventional planner Au electrode. In this study, electrochemical evaluation of cytochrome c was performed using the AuNP thin film electrodes with and without self-assembled monolayer (SAM) modification to assess its practicality for protein electrochemistry. The 4-pyridinethiol- and 7-carboxy-1-heptanethiol-modified AuNP thin film electrodes showed much larger faradaic current values attributed to redox reactions compared to those of the Au electrodes. The results indicate that the nanostructural effects of the AuNP thin film electrode are beneficial. Importantly, even when the non-modified (bare) AuNP thin film electrode was applied, it exhibited the clear electrochemical response of cyt c, while the bare Au electrode showed no such a response. This study provides evidence that the AuNP thin film electrode functions as a potent bioelectrocatalysts due to the nanostructure-specific properties.

Electrogenerated Chemiluminescence Imaging of Single‐Atom Nanocatalysts

AbstractSingle‐atom catalysts (SACs), distinguished by their maximum atom efficiency and precise control over the coordination and electronic properties of individual atoms, show great promise in electrocatalysis. Gaining a comprehensive understanding of the electrochemical performance of SACs requires the screening of electron transfer process at micro/nano scale. This research pioneers the use of electrogenerated chemiluminescence microscopy (ECLM) to observe the electrocatalytic reactions at individual SACs. It boasts sensitivity at the single photon level and temporal resolution down to 100 ms, enabling real‐time capture of the electrochemical behavior of individual SACs during potential sweeping. Leveraging the direct correlation between ECL emission and heterogeneous electron transfer processes, we introduced photon flux density for quantitative analysis, unveiling the electrocatalytic efficiency of individual SACs. This approach systematically reveals the relationship between SACs based on different metal atoms and their peroxidase (POD)‐like activity. The outcomes contribute to a fundamental understanding of SACs and pave the way for designing SACs with diverse technological and industrial applications.