Non-Markovian diffusion of excitons in layered perovskites and transition metal dichalcogenides.

The diffusion of excitons in perovskites and transition metal dichalcogenides shows clear anomalous, subdiffusive behaviour in experiments. In this paper we develop a non-Markovian mobile-immobile model which provides an explanation of this behaviour through paired theoretical and simulation approaches. The simulation model is based on a random walk on a 2D lattice with randomly distributed deep traps such that the trapping time distribution involves slowly decaying power-law asymptotics. The theoretical model uses coupled diffusion and rate equations for free and trapped excitons, respectively, with an integral term responsible for trapping. The model provides a good fitting of the experimental data, thus, showing a way for quantifying the exciton diffusion dynamics.

The Impact of Backbone Fluorination and Side-Chain Position in Thiophene-Benzothiadiazole-Based Hole-Transport Materials on the Performance and Stability of Perovskite Solar Cells.

Perovskite solar cells (PSCs) currently reach high efficiencies, while their insufficient stability remains an obstacle to their technological commercialization. The introduction of hole-transport materials (HTMs) into the device structure is a key approach for enhancing the efficiency and stability of devices. However, currently, the influence of the HTM structure or properties on the characteristics and operational stability of PSCs remains insufficiently studied. Herein, we present four novel push-pull small molecules, H1-4, with alternating thiophene and benzothiadiazole or fluorine-loaded benzothiadiazole units, which contain branched and linear alkyl chains in the different positions of terminal thiophenes to evaluate the impact of HTM structure on PSC performance. It is demonstrated that minor changes in the structure of HTMs significantly influence their behavior in thin films. In particular, H3 organizes into highly ordered lamellar structures in thin films, which proves to be crucial in boosting the efficiency and stability of PSCs. The presented results shed light on the crucial role of the HTM structure and the morphology of films in the performance of PSCs.

Hydroxyl Defects in LiFePO4 Cathode Material: DFT+U and an Experimental Study.

Lithium iron phosphate, LiFePO4, a widely used cathode material in commercial Li-ion batteries, unveils a complex defect structure, which is still being deciphered. Using a combined computational and experimental approach comprising density functional theory (DFT)+U and molecular dynamics calculations and X-ray and neutron diffraction, we provide a comprehensive characterization of various OH point defects in LiFePO4, including their formation, dynamics, and localization in the interstitial space and at Li, Fe, and P sites. It is demonstrated that one, two, and four (five) OH groups can effectively stabilize Li, Fe, and P vacancies, respectively. The presence of D (H) at both Li and P sites for hydrothermally synthesized deuterium-enriched LiFePO4 is confirmed by joint X-ray and neutron powder diffraction structure refinement at 5 K that also reveals a strong deficiency of P of 6%. The P occupancy decrease is explained by the formation of hydrogarnet-like P/4H and P/5H defects, which have the lowest formation energies among all considered OH defects. Molecular dynamics simulation shows a rich structural diversity of these defects, with OH groups pointing both inside and outside vacant P tetrahedra creating numerous energetically close conformers, which hinders their explicit localization with diffraction-based methods solely. The discovered conformers include structural water molecules, which are only by 0.04 eV/atom H higher in energy than separate OH defects.

Spatial determinants of quorum signaling in a Pseudomonas aeruginosa infection model.

Quorum sensing (QS) is a bacterial communication system that involves production and sensing of extracellular signals. In laboratory models, QS allows bacteria to monitor and respond to their own cell density and is critical for fitness. However, how QS proceeds in natural, spatially structured bacterial communities is not well understood, which significantly hampers our understanding of the emergent properties of natural communities. To address this gap, we assessed QS signaling in the opportunistic pathogen Pseudomonas aeruginosa in a cystic fibrosis (CF) lung infection model that recapitulates the biogeographical aspects of the natural human infection. In this model, P. aeruginosa grows as spatially organized, highly dense aggregates similar to those observed in the human CF lung. By combining this natural aggregate system with a micro-3D-printing platform that allows for confinement and precise spatial positioning of P. aeruginosa aggregates, we assessed the impact of aggregate size and spatial positioning on both intra- and interaggregate signaling. We discovered that aggregates containing ∼2,000 signal-producing P. aeruginosa were unable to signal neighboring aggregates, while those containing ≥5,000 cells signaled aggregates as far away as 176 µm. Not all aggregates within this "calling distance" responded, indicating that aggregates have differential sensitivities to signal. Overexpression of the signal receptor increased aggregate sensitivity to signal, suggesting that the ability of aggregates to respond is defined in part by receptor levels. These studies provide quantitative benchmark data for the impact of spatial arrangement and phenotypic heterogeneity on P. aeruginosa signaling in vivo.

Active learning-based framework for optimal reaction mechanism selection from microkinetic modeling: a case study of electrocatalytic oxygen reduction reaction on carbon nanotubes.

The elucidation of complex electrochemical reaction mechanisms requires advanced models with many intermediate reaction steps, which are governed by a large number of parameters like reaction rate constants and charge transfer coefficients. Overcomplicated models introduce high uncertainty in the choice of the parameters and cannot be used to obtain meaningful insights on the reaction pathway. We describe a new framework of optimal reaction mechanism selection based on the mean-field microkinetic modeling approach (MF-MKM) and adaptive sampling of model parameters. The optimal model is selected to provide both the accurate fitting of experimental data within the experimental error and low uncertainty of model parameters choice. Generally, this approach can be applied for any complex heterogeneous electrochemical reaction. We use the "2e-" electrocatalytic oxygen reduction reaction (ORR) on carbon nanotubes (CNTs) as a representative example of a sufficiently complex reaction. Rotating disk electrode (RDE) experimental data for both ORR in O2-saturated 0.1 M KOH solution and hydrogen peroxide oxidation/reduction reaction (HPRR/HPOR) in Ar-purged 0.1 M KOH solution with different HO2- concentrations were used to show the dependence of the model parameters uniqueness on the completeness of the experimental dataset. It is demonstrated that the optimal reaction mechanism for ORR on CNT and available experimental data consists of O2 adsorption step on the electrode surface and effective step of two-electron reduction to HO2- combined with its desorption from the electrode. The low uncertainty of estimated model parameters is provided only within the 2-step model being applied to the full available experimental dataset. The assessment of elementary step mechanisms on electro-catalytic materials including carbon-based electrodes requires more diverse experimental data and/or higher precision of experimental measurements to facilitate more precise microkinetic modeling of more complex reaction mechanisms.

Thermal Effects and Halide Mixing of Hybrid Perovskites: MD and XPS Studies.

Thermal effects in organo-metal halide perovskites are studied by ab initio molecular dynamics (MD) simulations performed at effective temperatures of 293 and 383 K and by X-ray photoelectron spectroscopy (XPS). We find that the cause of thermal instability in this class of perovskites is the rotation of the methylammonium (MA) groups that destroy the rigid lattice of pure compounds (MAPbI3 and MAPbBr3). When the Pb-I lattice is initially distorted by partial replacement of the I with Cl or Br, this not only prevents formation of PbI2 seeds but also improves lattice flexibility and stability against the temperature-induced motion and rotation of MA groups.

Origins of irreversible capacity loss in hard carbon negative electrodes for potassium-ion batteries.

Hard carbon (HC) is considered as a negative electrode material for potassium-ion batteries, but it suffers from significant irreversible capacity loss at the first discharge cycle. Here, we investigated the possible reasons of this capacity loss with a combination of in situ AFM and various ex situ TEM techniques (high resolution TEM and high angle annular dark field scanning TEM imaging, and STEM-EELS and STEM-EDX spectroscopic mapping) targeting the electrode/electrolyte interphase formation process in the carbonate-based electrolyte with and without vinylene carbonate (VC) as an additive. The studied HC consists of curved graphitic layers arranged into short packets and round cages, the latter acting as traps for K+ ions causing low Coulombic efficiency between cycling. Our comparative study of solid electrolyte interphase (SEI) formation in the carbonate-based electrolyte with and without the VC additive revealed that in the pristine electrolyte, the SEI consists mostly of inorganic components, whereas adding VC introduces a polymeric organic component to the SEI, increasing its elasticity and stability against fracturing upon HC expansion/contraction during electrochemical cycling. Additionally, significant K+ loss occurs due to Na+ for K+ exchange in Na-carboxymethyl cellulose used as a binder. These findings reflect the cumulative impact of the internal HC structure, SEI properties, and binder nature into the electrochemical functional properties of the HC-based anodes for K-ion batteries.

Electrochemical sensors for rapid diagnosis of pathogens in real time.

Microbial infections remain the principal cause for high morbidity and mortality rates. While approximately 1400 human pathogens have been recognized, the majority of healthcare-associated infectious diseases are caused by only a few opportunistic pathogens (e.g., Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli), which are associated with increased antibiotic and antimicrobial resistance. Rapid detection, reliable identification and real-time monitoring of these pathogens remain not only a scientific problem but also a practical challenge of vast importance, especially in tailoring effective treatment strategies. Although the development of vaccinations and antibacterial drug treatments are the leading research, progress, and implementation of early warning, quantitative systems indicative of confirming pathogen presence are necessary. Over the years, various approaches, such as conventional culturing, straining, molecular methods (e.g., polymerase chain reaction and immunological assays), microscopy-based and mass spectrometry techniques, have been employed to identify and quantify pathogenic agents. While being sensitive in some cases, these procedures are costly, time-consuming, mostly qualitative, and are indirect detection methods. A great challenge is therefore to develop rapid, highly sensitive, specific devices with adequate figures of merit to corroborate the presence of microbes and enable dynamic real-time measurements of metabolism. As an alternative, electrochemical sensor platforms have been developed as powerful quantitative tools for label-free detection of infection-related biomarkers with high sensitivity. This minireview is focused on the latest electrochemical-based approaches for pathogen sensing, putting them into the context of standard sensing methods, such as cell culturing, mass spectrometry, and fluorescent-based approaches. Description of the latest, impactful electrochemical sensors for pathogen detection will be presented. Recent breakthroughs will be highlighted, including the use of micro- and nano-electrode arrays for real-time detection of bacteria in polymicrobial infections and microfluidic devices for pathogen separation analysis. We will conclude with perspectives and outlooks to understand shortcomings in designing future sensing schemes. The need for high sensitivity and selectivity, low-cost implementation, fast detection, and screening increases provides an impetus for further development in electrochemical detectors for microorganisms and biologically relevant targets.

Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La1-xSrxCoO3-δ perovskite composite electrodes.

Perovskite oxides are active room-temperature bifunctional oxygen electrocatalysts in alkaline media, capable of performing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with lower combined overpotentials relative to their precious metal counterparts. However, their semiconducting nature necessitates the use of activated carbons as conductive supports to generate applicably relevant current densities. In efforts to advance the performance and theory of oxide electrocatalysts, the chemical and physical properties of the oxide material often take precedence over contributions from the conductive additive. In this work, we find that carbon plays an important synergistic role in improving the performance of La1-xSrxCoO3-δ (0 ≤ x ≤ 1) electrocatalysts through the activation of O2 and spillover of radical oxygen intermediates, HO2- and O2-, which is further reduced through chemical decomposition of HO2- on the perovskite surface. Through a combination of thin-film rotating disk electrochemical characterization of the hydrogen peroxide intermediate reactions (hydrogen peroxide reduction reaction (HPRR), hydrogen peroxide oxidation reaction (HPOR)) and oxygen reduction reaction (ORR), surface chemical analysis, HR-TEM, and microkinetic modeling on La1-xSrxCoO3-δ (0 ≤ x ≤ 1)/carbon (with nitrogen and non-nitrogen doped carbons) composite electrocatalysts, we deconvolute the mechanistic aspects and contributions to reactivity of the oxide and carbon support.

Cobalt and Vanadium Trimetaphosphate Polyanions: Synthesis, Characterization, and Electrochemical Evaluation for Non-aqueous Redox-Flow Battery Applications.

An electrochemical cell consisting of cobalt ([CoII/III(P3O9)2]4-/3-) and vanadium ([VIII/II(P3O9)2]3-/4-) bistrimetaphosphate complexes as catholyte and anolyte species, respectively, was constructed with a cell voltage of 2.4 V and Coulombic efficiencies >90% for up to 100 total cycles. The [Co(P3O9)2]4- (1) and [V(P3O9)2]3- (2) complexes have favorable properties for flow-battery applications, including reversible redox chemistry, high stability toward electrochemical cycling, and high solubility in MeCN (1.09 ± 0.02 M, [PPN]4[1]·2MeCN; 0.77 ± 0.06 M, [PPN]3[2]·DME). The [PPN]4[1]·2MeCN and [PPN]3[2]·DME salts were isolated as crystalline solids in 82 and 68% yields, respectively, and characterized by 31P NMR, UV/vis, ESI-MS(-), and IR spectroscopy. The [PPN]4[1]·2MeCN salt was also structurally characterized, crystallizing in the monoclinic P21/c space group. Treatment of 1 with [(p-BrC6H4)3N]+ allowed for isolation of the one-electron-oxidized spin-crossover (SCO) complex, [Co(P3O9)2]3- (3), which is the active catholyte species generated during cell charging. The success of the 1-2 cell provides a promising entry point to a potential future class of transition-metal metaphosphate-based all-inorganic non-aqueous redox-flow battery electrolytes.

The Role of Semilabile Oxygen Atoms for Intercalation Chemistry of the Metal-Ion Battery Polyanion Cathodes.

Using the orthorhombic layered Na2FePO4F cathode material as a model system we identify the bonding of the alkali metal cations to the semilabile oxygen atoms as an important factor affecting electrochemical activity of alkali cations in polyanion structures. The semilabile oxygens, bonded to the P and alkali cations, but not included into the FeO4F2 octahedra, experience severe undercoordination upon alkali cation deintercalation, causing an energy penalty for removing the alkali cations located in the proximity of such semilabile oxygens. Desodiation of Na2FePO4F proceeds through a two-phase mechanism in the Na-ion cell with a formation of an intermediate monoclinic Na1.55FePO4F phase with coupled Na/vacancy and Fe2+/Fe3+ charge ordering at 50% state of charge. In contrast, desodiation of Na2FePO4F in the Li-ion cell demonstrates a sloping charge profile suggesting a solid solution mechanism without formation of a charge-ordered intermediate phase. A combination of a comprehensive crystallographic study and extensive DFT-based calculations demonstrates that the difference in electrochemical behavior of the alkali cation positions is largely related to the different number of the nearest neighbor semilabile oxygen atoms, influencing their desodiation potential and accessibility for the Na/Li chemical exchange, triggering coupled alkali cation-vacancy ordering and Fe2+/Fe3+ charge ordering, as well as switching between the "solid solution" and "two-phase" charging mechanistic regimes.

A Novel Family of Polyiodo-Bromoantimonate(III) Complexes: Cation-Driven Self-Assembly of Photoconductive Metal-Polyhalide Frameworks.

In the presence of different cations, reactions of [SbBr6 ]3- and I2 result in a new family of diverse supramolecular 1D polyiodide-bromoantimonate networks. The coordination number of Sb, as well as geometry of assembling {Ix }n- polyhalide units, can vary, resulting in unprecedented structural types. The nature of I⋅⋅⋅Br interactions was studied by DFT calculations; estimated energy values are 1.6-6.9 kcal mol-1 . Some of the compounds showed strong photoconductivity in thin films, suggesting multiple feasible applications in optoelectronics and solar energy conversion.

On the Origin of Extended Resolution in Kelvin Probe Force Microscopy with a Worn Tip Apex.

In this work we analyzed the effect of the atomic force microscopy probe tip apex shape on Kelvin Probe Force Microscopy (KPFM) potential sensitivity and spatial resolution. It was found that modification of the apex shape from spherical to planar upon thinning of the conductive coating leads to enhanced apex contribution to the total electrostatic force between the probe and the sample. The effect results in extended potential sensitivity and spatial resolution of KPFM. Experimental results were supported by calculations.

Transparent Carbon Ultramicroelectrode Arrays for the Electrochemical Detection of a Bacterial Warfare Toxin, Pyocyanin.

Pyocyanin is a virulence factor produced as a secondary metabolite by the opportunistic human pathogen, Pseudomonas aeruginosa. Fast and direct detection of pyocyanin is of importance as it could provide important insights regarding P. aeruginosa's virulence mechanisms. Here, we present an electrochemical sensing platform of redox-active pyocyanin using transparent carbon ultramicroelectrode arrays (T-CUAs), which were made using a previously reported simple fabrication process ( Duay et al. Anal. Chem. 2015 , 87 , 10109 ). Square-wave voltammetry was used to quantify pyocyanin concentrations on T-CUAs with and without chitosan gold nanoparticles (CS/GNP) and planar transparent macroelectrodes (T-Macro). The response time (RT), limit of detection (LOD), and linear dynamic range (LDR) differ for each electrode type due to subtle influences in how the detectable signal varies in relation to the charging time and resistive and capacitive noise. In general lower LODs can be achieved at the consequence of smaller LDRs. The LOD for T-Macro was 0.75 ± 0.09 µM with a LDR of 0.75-25 µM, and the LOD for the CS/GNP 1.54 T-CUA was determined to be 1.6 ± 0.2 µM with a LDR of 1-100 µM, respectively. The LOD for the 1.54T-CUA with a larger LDR of 1-250 µM was 1.0 ± 0.3 µM. These LODs and LDRs fall within the range of PYO concentrations for a variety of in vitro and in vivo cellular environments and offer promise of the application of T-CUAs for the quantitative study of biotoxins, quorum sensing, and pathogenesis. Finally, we demonstrate the successful use of T-CUAs for the electrochemical detection of pyocyanin secreted from P. aeruginosa strains while optically imaging the cells. The secreted pyocyanin levels from two bacterial strains, PA11 and PA14, were measured to have concentrations of 45 ± 5 and 3 ± 2 µM, respectively.

Gold Nanoparticle Modified Transparent Carbon Ultramicroelectrode Arrays for the Selective and Sensitive Electroanalytical Detection of Nitric Oxide.

Transparent carbon ultramicroelectrode arrays (T-CUAs) were made using a previously reported facile fabrication method (Duay et al. Anal. Chem. 2015, 87, 10109). Two modifications introduced to the T-CUAs were examined for their analytical response to nitric oxide (NO•). The first modification was the application of a cellulose acetate (CA) gas permeable membrane. Its selectivity to NO• was extensively characterized via chronoamperometry, electrochemical impedance spectroscopy (EIS), and atomic force microscopy (AFM). The thickness of the CA membrane was determined to be 100 nm and 88 ± 15 nm using AFM and EIS, respectively. Furthermore, the partition and diffusion coefficients of NO• within the CA membrane were determined to be 0.0500 and 2.44 × 10-13 m2/s using EIS measurements. The second modification to the 1.54T-CUA was the introduction of chitosan and gold nanoparticles (CS/GNPs) to enhance its catalytic activity, sensitivity, and limit of detection (LOD) to NO•. Square wave voltammetry was used to quantify the NO• concentration at the CA membrane covered 1.54T-CUA with and without CS/GNPs; the LODs were determined to be 0.2 ± 0.1 and 0.44 ± 0.02 µM (S/N = 3), with sensitivities of 9 ± 9 and 1.2 ± 0.4 nA/µM, respectively. Our results indicate that this modification to the arrays results in a significant catalytic enhancement to the electrochemical oxidation of NO•. Hence, these electrodes allow for the in situ mechanistic and kinetic characterization of electrochemical reactions with high electroanalytical sensitivity.

Electrodeposition of Amorphous Molybdenum Chalcogenides from Ionic Liquids and Their Activity for the Hydrogen Evolution Reaction.

This work reports on the general electrodeposition mechanism of tetrachalcogenmetallates from 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Both tetrathio- and tetraselenomolybdate underwent anodic electrodeposition and cathodic corrosion reactions as determined by UV-vis spectroelectrochemistry. Electrodeposition was carried out by cycling the potential between the anodic and cathodic regimes. This resulted in a film of densely packed nanoparticles of amorphous MoSx or MoSex as determined by SEM, Raman, and XPS. The films were shown to have high activity for the hydrogen evolution reaction. The onset potential (J = 1 mA/cm2) of the MoSx film was E = -0.208 V vs RHE, and that of MoSex was E = -0.230 V vs RHE. The Tafel slope of MoSx was 42 mV/decade, and that of MoSex was 59 mV/decade.

Lithium Ion Coupled Electron-Transfer Rates in Superconcentrated Electrolytes: Exploring the Bottlenecks for Fast Charge-Transfer Rates with LiMn2O4 Cathode Materials.

The charge-transfer kinetics of lithium ion intercalation into LixMn2O4 cathode materials was examined in dilute and concentrated aqueous and carbonate LiTFSI solutions using electrochemical methods. Distinctive trends in ion intercalation rates were observed between water-based and ethylene carbonate/diethyl carbonate solutions. The influence of the solution concentration on the rate of lithium ion transfer in aqueous media can be tentatively attributed to the process associated with Mn dissolution, whereas in carbonate solutions the rate is influenced by the formation of a concentration-dependent solid electrolyte interface (SEI). Some indications of SEI layer formation at electrode surfaces in carbonate solutions after cycling are detected by X-ray photoelectron spectroscopy. The general consequences related to the application of superconcentrated electrolytes for use in advanced energy storage cathodes are outlined and discussed.

Transparent carbon ultramicroelectrode arrays: figures of merit for quantitative spectroelectrochemistry for biogenic analysis of reactive oxygen species.

Opaque and transparent carbon ultramicro- to nanoelectrode arrays were made using a previously reported facile versatile fabrication method (Duay et al. Anal. Chem. 2014, 86, 11528). First, opaque carbon ultramicroelectrode arrays (CUAs) were characterized for their analytical response to hydrogen peroxide (H2O2) oxidation using cyclic voltammetry. The alumina blocking layer was found to contribute to the noise and thus had undesirable effects on the array's limit of detection (LOD) for H2O2 at fast scan rates. Nonetheless, at slower scan rates (ν ≤ 250 mV s(-1)), the LODs for H2O2 for both opaque (O-CUAs) and transparent arrays (T-CUAs) were found to be lower than previously reported levels for array-based UMEs. LODs as low as 35 nM H2O2 are obtained for T-CUA at a 2.5 mV s(-1) scan rate. Furthermore, the transparent arrays were analyzed for their spectroelectrochemical response during the oxidation/reduction of ferrocenemethanol. Results showed very good correlation between the optical and electrochemical response for ferrocenemethanol at a UV wavelength of 254 nm. Thus, these electrodes allow for the in situ mechanistic and kinetic characterization of heterogeneous electrochemical and intermediate homogeneous chemical reactions with high electroanalytical sensitivity, low detection limits, and wide dynamic range.

Amperometric Detection of Aqueous Silver Ions by Inhibition of Glucose Oxidase Immobilized on Nitrogen-Doped Carbon Nanotube Electrodes.

An amperometric glucose biosensor based on immobilization of glucose oxidase on nitrogen-doped carbon nanotubes (N-CNTs) was successfully developed for the determination of silver ions. Upon exposure to glucose, a steady-state enzymatic turnover rate was detected through amperometric oxidation of the H2O2 byproduct, directly related to the concentration of glucose in solution. Inhibition of the steady-state enzymatic glucose oxidase reaction by heavy metals ions such as Ag(+), produced a quantitative decrease in the steady-state rate, subsequently creating an ultrasensitive metal ion biosensor through enzymatic inhibition. The Ag(+) biosensor displayed a sensitivity of 2.00 × 10(8) ± 0.06 M(-1), a limit of detection (σ = 3) of 0.19 ± 0.04 ppb, a linear range of 20-200 nM, and sample recovery at 101 ± 2%, all acquired at a low-operating potential of 0.05 V (vs Hg/Hg2SO4). Interestingly, the biosensor does not display a loss in sensitivity with continued use due to the % inhibition based detection scheme: loss of enzyme (from continued use) does not influence the % inhibition, only the overall current associated with the activity loss. The heavy metals Cu(2+) and Co(2+) were also detected using the enzyme biosensor but found to be much less inhibitory, with sensitivities of 1.45 × 10(6) ± 0.05 M(-1) and 2.69 × 10(3) ± 0.07 M(-1), respectively. The mode of GOx inhibition was examined for both Ag(+) and Cu(2+) using Dixon and Cornish-Bowden plots, where a strong correlation was observed between the inhibition constants and the biosensor sensitivity.

H2O2 Detection at Carbon Nanotubes and Nitrogen-Doped Carbon Nanotubes: Oxidation, Reduction, or Disproportionation?

The electrochemical behavior of hydrogen peroxide (H2O2) at carbon nanotubes (CNTs) and nitrogen-doped carbon nanotubes (N-CNTs) was investigated over a wide potential window. At CNTs, H2O2 will be oxidized or reduced at large overpotentials, with a large potential region between these two processes where electrochemical activity is negligible. At N-CNTs, the overpotential for both H2O2 oxidation and reduction is significantly reduced; however, the reduction current from H2O2, especially at low overpotentials, is attributed to increased oxygen reduction rather than the direct reduction of H2O2, due to a fast chemical disproportionation of H2O2 at the N-CNT surface. Additionally, N-CNTs do not display separation between observable oxidation and reduction currents from H2O2. Overall, the analytical sensitivity of N-CNTs to H2O2, either by oxidation or reduction, is considerably higher than CNTs, and obtained at significantly lower overpotentials. N-CNTs display an anodic sensitivity and limit of detection of 830 mA M(-1) cm(-2) and 0.5 µM at 0.05 V, and a cathodic sensitivity and limit of detection of 270 mA M(-1) cm(-2) and 10 µM at -0.25 V (V vs Hg/Hg2SO4). N-CNTs are also a superior platform for the creation of bioelectrodes from the spontaneous adsorption of enzyme, compared to CNTs. Glucose oxidase (GOx) was allowed to adsorb onto N-CNTs, producing a bioelectrode with a sensitivity and limit of detection to glucose of 80 mA M(-1) cm(-2) and 7 µM after only 30 s of adsorption time from a 81.3 µM GOx solution.