Voltage-Driven Molecular Photoelectrocatalysis of Water Oxidation.

Molecular photocatalysis and photoelectrocatalysis have been widely used to conduct oxidation-reduction processes ranging from fuel generation to electroorganic synthesis. We recently showed that an electrostatic potential drop across the double layer contributes to the driving force for electron transfer (ET) between a dissolved reactant and a molecular catalyst immobilized directly on the electrode surface. In this article, we report voltage-driven molecular photoelectrocatalysis with a prevalent homogeneous water oxidation catalyst, (bpy)Cu (II), which was covalently attached to the carbon surface and exhibited photocatalytic activity. The strong potential dependence of the photooxidation current suggests that the electrostatic potential drop across the double layer contributes to the driving force for ET between a water molecule and the excited state of surface-bound (bpy)Cu (II). Scanning electrochemical microscopy (SECM) was used to analyze the products and determine the faradaic efficiencies for the generation of oxygen and hydrogen peroxide. Unlike electrocatalytic water oxidation by (bpy)Cu (II) in the dark, which produces only O2, the voltage-driven photooxidation includes an additional 2e- pathway generating H2O2. DFT calculations show that the applied voltage and the presence of light can alter the activation energy for the rate-determining water nucleophilic attack steps, thereby increasing the reaction rate of photo-oxidation of water and opening the 2e- pathway. These results suggest a new route for designing next-generation hybrid molecular photo(electro)catalysts for water oxidation and other processes.

Quantitative Measurements of Electrocatalytic Reaction Rates with NanoSECM.

Scanning electrochemical microscopy (SECM) has been extensively used for mapping electrocatalytic surface reactivity; however, most of the studies were carried out using micrometer-sized tips, and no quantitative kinetic experiments on the nanoscale have yet been reported to date. As the diffusion-limited current density at a nanometer-sized electrode is very high, an inner-sphere electron-transfer process occurring at a nanotip typically produces a kinetic current at any attainable overpotential. Here, we develop a theory for substrate generation/tip collection (SG/TC) and feedback modes of SECM with a kinetic tip current and use it to evaluate the rates of hydrogen and oxygen evolution reactions in a neutral aqueous solution from the current-distance curves. The possibility of using chemically modified nanotips for kinetic measurements is also demonstrated. The effect of the substrate size on the shape of the current-distance curves in SG/TC mode SECM experiments is discussed.

Efficient Voltage-Driven Oxidation of Water and Alcohols by an Organic Molecular Catalyst Directly Attached to a Carbon Electrode.

The integration of heterogeneous electrocatalysis and molecular catalysis is a promising approach to designing new catalysts for the oxygen evolution reaction (OER) and other processes. We recently showed that the electrostatic potential drop across the double layer contributes to the driving force for electron transfer between a dissolved reactant and a molecular catalyst immobilized directly on the electrode surface. Here, we report high current densities and low onset potentials for water oxidation attained using a metal-free voltage-assisted molecular catalyst (TEMPO). Scanning electrochemical microscopy (SECM) was used to analyze the products and determine faradic efficiencies for the generation of H2O2 and O2. The same catalyst was employed for efficient oxidations of butanol, ethanol, glycerol, and H2O2. DFT calculations show that the applied voltage alters the electrostatic potential drop between TEMPO and the reactant as well as chemical bonding between them, thereby increasing the reaction rate. These results suggest a new route for designing next-generation hybrid molecular/electrocatalysts for OER and alcohol oxidations.

Photo-scanning Electrochemical Microscopy Observation of Overall Water Splitting at a Single Aluminum-Doped Strontium Titanium Oxide Microcrystal.

Particulate photocatalysts for the overall water splitting (OWS) reaction offer promise as devices for hydrogen fuel generation. Even though such photocatalysts have been studied for nearly 5 decades, much of the understanding of their function is derived from observations of catalyst ensembles and macroscopic photoelectrodes. This is because the sub-micrometer size of most OWS photocatalysts makes spatially resolved measurements of their local reactivity very difficult. Here, we employ photo-scanning electrochemical microscopy (photo-SECM) to quantitatively measure hydrogen and oxygen evolution at individual OWS photocatalyst particles for the first time. Micrometer-sized Al-doped SrTiO3/Rh2-yCryO3 photocatalyst particles were immobilized on a glass substrate and interrogated with a chemically modified SECM nanotip. The tip simultaneously served as a light guide to illuminate the photocatalyst and as an electrochemical nanoprobe to observe oxygen and hydrogen fluxes from the OWS. Local O2 and H2 fluxes obtained from chopped light experiments and photo-SECM approach curves using a COMSOL Multiphysics finite-element model confirmed stoichiometric H2/O2 evolution of 9.3/4.6 µmol cm-2 h-1 with no observable lag during chopped illumination cycles. Additionally, photoelectrochemical experiments on a single microcrystal attached to a nanoelectrode tip revealed a strong light intensity dependence of the OWS reaction. These results provide the first confirmation of OWS at single micrometer-sized photocatalyst particles. The developed experimental approach is an important step toward assessing the activity of photocatalyst particles at the nanometer scale.

Voltage-Driven Molecular Catalysis of Electrochemical Reactions.

Heterogeneous electrocatalysis and molecular redox catalysis have developed over several decades as two distinct ways to facilitate charge-transfer processes essential for energy conversion and storage. Whereas electrocatalytic reactions are driven by the applied voltage, molecular catalytic processes are driven by the difference between standard potentials of the catalyst and the reactant. Here, we demonstrate that the rate of electron transfer between a dissolved reactant and a molecular catalyst immobilized directly on the surface of a carbon nanoelectrode is governed by combination of chemical driving force and electrostatic potential drop across the double layer. DFT calculations show that varying the applied voltage alters the potential drop between the surface-bound and dissolved redox species. These results suggest a new route for designing next-generation hybrid molecular/electrocatalysts.

Mediated Charge Transfer at Nanoelectrodes: A New Approach to Electrochemical Reactivity Mapping and Nanosensing.

Scanning electrochemical microscopy (SECM) is a powerful tool for mapping surface reactivity. Electrochemical mapping of electrocatalytic processes at the nanoscale is, however, challenging because the surface of a nanoelectrode tip is easily fouled by impurities and/or deactivated by products and intermediates of innersphere surface reactions. To overcome this difficulty, we introduce new types of SECM nanotips based on bimolecular electron transfer between the dissolved electroactive species and a redox mediator attached to the surface of a carbon nanoelectrode. A tris(2,2'-bipyridine)ruthenium complex, Ru(bpy)3, that undergoes reversible oxidation/reduction reactions at both positive and negative potentials was used to prepare the SECM nanoprobes for mapping a wide range of electrocatalytic processes through oxidation of H2, reduction of O2, and both oxidation and reduction of H2O2 at the tip. In addition to high-resolution reactivity mapping and localized kinetic measurements, chemically modified nanoelectrodes can serve as nanosensors for a number of important analytes such as reactive oxygen and nitrogen species and neurotransmitters.

Visualization of Hydrogen Evolution at Individual Platinum Nanoparticles at a Buried Interface.

Electrochemical processes occurring at solid/solid and solid/membrane interfaces govern the behavior of a variety of energy storage devices, including electrocatalytic reactions at electrode/membrane interfaces in fuel cells and ion insertion at electrode/electrolyte interfaces in solid-state batteries. Due to the heterogeneity of these systems, interrogation of interfacial activity at nanometer length scales is desired to understand system performance, yet the buried nature of the interfaces makes localized activity inaccessible to conventional electrochemical techniques. Herein, we demonstrate nanoscale electrochemical imaging of hydrogen evolution at individual Pt nanoparticles (PtNPs) positioned at a buried interface using scanning electrochemical cell microscopy (SECCM). Specifically, we image the hydrogen evolution reaction (HER) at individual carbon-supported PtNP electrocatalysts covered by a 100 to 800 nm thick layer of the proton exchange membrane Nafion. The rate of hydrogen evolution at PtNP at this buried interface is shown to be a function of Nafion thickness, with the highest activity observed for ∼200 nm thick films.

Electrochemical Generation of Individual Nanobubbles Comprising H2, D2, and HD.

The electrochemical reduction of deuterons (2D+ + 2e- → D2) at Pt nanodisk electrodes (radius = 15-100 nm) in D2O solutions containing deuterium chloride (DCl) results in the formation of a single gas nanobubble at the electrode surface. Analogous to that previously observed for the electrochemical generation of H2 nanobubbles, the nucleation and growth of a stable D2 nanobubble is characterized in voltammetric experiments by a highly reproducible and well-resolved sudden drop in the faradaic current, a consequence of restricted mass transport of D+ to the electrode surface following the liquid-to-gas phase transition. D2 nanobubbles are stable under potential control due to a dynamic equilibrium existing between D2 gas dissolution and electrochemical generation of D2 at the circumference of the Pt nanodisk electrode. Remarkably, within the error of the experimental measurement (<6%), the electrochemical current required to nucleate a D2 gas phase in a D2O solution is identical to that for the H2 gas phase in a H2O solutions, indicating that the concentration required for nucleating a D2 nanobubble in D2O (0.29 M) is ∼1.25 times larger than that for a H2 nanobubble (0.23 M), while the supersaturation is ∼300 in each case. We further demonstrate that individual nanobubbles can be electrogenerated in mixed D2O/H2O solutions containing both D+ and H+ at respective individual concentrations well below those required to nucleate a gas phase containing either pure D2 or H2. This latter finding indicates that the resulting nanobubbles comprise a mixture of D2, H2, and HD molecules with the chemical composition of a nanobubble determined by the concentrations and diffusivities of D+ and H+ in the mixed D2O/H2O solutions.

Electrochemically Driven, Ni-Catalyzed Aryl Amination: Scope, Mechanism, and Applications.

C-N cross-coupling is one of the most valuable and widespread transformations in organic synthesis. Largely dominated by Pd- and Cu-based catalytic systems, it has proven to be a staple transformation for those in both academia and industry. The current study presents the development and mechanistic understanding of an electrochemically driven, Ni-catalyzed method for achieving this reaction of high strategic importance. Through a series of electrochemical, computational, kinetic, and empirical experiments, the key mechanistic features of this reaction have been unraveled, leading to a second generation set of conditions that is applicable to a broad range of aryl halides and amine nucleophiles including complex examples on oligopeptides, medicinally relevant heterocycles, natural products, and sugars. Full disclosure of the current limitations and procedures for both batch and flow scale-ups (100 g) are also described.

Can the delayed effects of climatic oscillations have a greater influence on global fisheries compared to their immediate effects?

Climatic oscillations affect fish population dynamics, ecological processes, and fishing operations in maritime habitats. This study examined how climatic oscillations affect catch rates for striped, blue, and silver marlins in the Atlantic Ocean. These oscillations are regarded as the primary factor influencing the abundance and accessibility of specific resources utilized by fishers. Logbook data were obtained from Taiwanese large-scale fishing vessels for climatic oscillations during the period 2005-2016. The results indicated that the effect of the Subtropical Indian Ocean Dipole on marlin catch rates did not have a lag, whereas those of the North Atlantic Oscillation, Atlantic Multidecadal Oscillation, Pacific Decadal Oscillation, and Indian Ocean Dipole had various lags. Pearson's correlation analysis was conducted to examine the correlations between atmospheric oscillation indices and marlin catch rates, and wavelet analysis was employed to describe the influences of the most relevant lags. The results indicated that annual atmospheric fluctuations and their lags affected the abundance and catchability of striped, blue, and silver marlins in the study region. This, in turn, may affect the presence of these species in the market and lead to fluctuations in their prices in accordance with supply and demand. Overall, understanding the effects of climatic oscillations on fish species are essential for policymakers and coastal communities seeking to manage marine resources, predict changes in marine ecosystems, and establish appropriate methods for controlling the effects of climate variability.

Visualizing Overall Water Splitting on Single Microcrystals of Phosphorus-Doped BiVO4 by Photo-SECM.

Particulate bismuth vanadate (BiVO4) has attracted considerable interest as a promising photo(electro)catalyst for visible-light-driven water oxidation; however, overall water splitting (OWS) has been difficult to attain because its conduction band is too positive for efficient hydrogen evolution. Using photoscanning electrochemical microscopy (photo-SECM) with a chemically modified nanotip, we visualized for the first time the OWS at a single truncated bipyramidal microcrystal of phosphorus-doped BiVO4. The tip simultaneously served as a light guide to illuminate the photocatalyst and an electrochemical nanoprobe to observe and quantitatively measure local oxygen and hydrogen fluxes. The obtained current patterns for both O2 and H2 agree well with the accumulation of photogenerated electrons and holes on {010} basal and {110} lateral facets, respectively. The developed experimental approach is an important step toward nanoelectrochemical mapping of the activity of photocatalyst particles at the subfacet level.

Electrocatalytic oxidation of water by the immobilized [CuII(l-ala)(Phen)(H2O)]+ complex on a self-assembled NCS- modified gold electrode.

Copper(ii) complex [CuII(l-ala)(Phen)(H2O)]+ (l-ala = l-phenylalanine, phen = phenanthroline) was immobilized over a self-assembled NCS- modified gold electrode for the electrocatalytic oxidation of water. This surface anchored molecular complex can catalyze water oxidation reaction at a remarkably low overpotential of 327 mV with a current density of 0.5 mA cm-2 at neutral pH.

Electrocatalytic oxidation of water at a polyoxometalate nanoparticle modified gold electrode.

Spherical polyoxometalate nanoparticles, [HPMo]NPs, were synthesized from a very well known Keggin-type polyoxometalate [H3PMo12O40] in the presence of sodium dodecyl sulphate (SDS) and polyvinyl pyrrolidine (PVP) in aqueous medium and characterized by UV-Vis spectroscopy and Transmission Electron Microscopy (TEM). The [HPMo]NPs were used to modify a gold working electrode and they were characterized by SEM, EDX, elemental mapping, cyclic voltammetry and electrochemical impedance spectroscopy and applied for the electrocatalytic oxidation of water in a phosphate buffer solution at neutral pH. The modified electrode showed excellent electrocatalytic activity towards oxidation of water at an impressively low overpotential ∼350 mV with a high current density of around 1.7 mA cm-2, good stability under exhaustive electrolysis conditions and also showed long term stability.

Synthesis of ultrasmall and monodisperse sulfur nanoparticle intercalated CoAl layered double hydroxide and its electro-catalytic water oxidation reaction at neutral pH.

Ultrasmall and monodisperse sulfur nanoparticle (S-NP) intercalated CoAl-layered double hydroxide (CoAl-LDH) electrocatalyst exhibits an excellent electrocatalytic activity towards water oxidation with a low overpotential of 250 mV at a high current density of 7.9 mA cm-2 and a Tafel slope of 61 mV dec-1 at the neutral pH condition. The fabrication strategy to achieve a high-performance, robust and durable electrocatalyst is a scale-up in next generation renewable energy fields.

Compatibility of Flavoring Agents in Compounding Extemporaneous Omeprazole Oral Liquid.

In a previous study, the results of which were provided in an article published in the International Journal of Pharmaceutical Compounding, it was determined that FLAVORx's Grape flavor in extemporaneously compounded omeprazole oral liquid was found suitable. A follow-up study was conducted in which the authors explored four additional flavors (Professional Compounding Centers of America's Cherry Concentrate and their Orange Concentrate, and FLAVORx's Bubble Gum flavor and their Watermelon flavor) to allow pharmacists and patients greater flexibility and options to flavor omeprazole oral liquid. Oral liquids were compounded using 20-mg omeprazole delayed-release capsules, 8.4% sodium bicarbonate, and each of four flavors to reach drug concentration at 2 mg/mL and flavor at 1.2% v/v (n=3). After the delayed-release pellets were disintegrated, the prescription bottles were stored in cold temperature overnight. For flavor alone in 8.4% sodium bicarbonate solution, samples were prepared the same as above except no omeprazole delayed-release capsules were added. High-performance liquid chromatographic assay was adopted from the United States Pharmacopeia's Omeprazole Monograph, but it is for the unflavored oral liquid. In order to ensure assay robustness, stability indication tests, 0.1 N HCl (acid), 0.1 N NaOH (base), 50°C (heat), and 3% hydrogen peroxide were also performed to the flavored omeprazole oral liquids, as well as to the individual flavor alone in sodium bicarbonate solution without omeprazole. Professional Compounding Centers of America's Cherry Concentrate, Orange Concentrate, and FLAVORx's Watermelon flavor showed no interference with the drug, and the assays were robust. However, FLAVORx's Bubble Gum flavor displayed five mini peaks at 280 nm with one embedded in omeprazole peak. The resolution of a Bubble Gum peak immediately next to an omeprazole peak computed by column kinetics was 0.91, while the separation factor was 1.15. A good separation is generally >1.5. This study examined only the Cherry Concentrate, Orange Concentrate, Bubble Gum flavor, and Watermelon flavor from the specified manufacturers. An insignificant interference was shown between FLAVORx's Bubble Gum flavor with omeprazole. The results are not intended to infer that all brands of the same flavor names would react the same way. Omeprazole and all four studied flavors should be protected from oxidation insult.

A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms.

Monitoring reactive intermediates can provide vital information in the study of synthetic reaction mechanisms, enabling the design of new catalysts and methods. Many synthetic transformations are centred on the alteration of oxidation states, but these redox processes frequently pass through intermediates with short life-times, making their study challenging. A variety of electroanalytical tools can be utilised to investigate these redox-active intermediates: from voltammetry to in situ spectroelectrochemistry and scanning electrochemical microscopy. This perspective provides an overview of these tools, with examples of both electrochemically-initiated processes and monitoring redox-active intermediates formed chemically in solution. The article is designed to introduce synthetic organic and organometallic chemists to electroanalytical techniques and their use in probing key mechanistic questions.

MnO doped SnO2 nanocatalysts: Activation of wide band gap semiconducting nanomaterials towards visible light induced photoelectrocatalytic water oxidation.

Semiconducting nanomaterials are very important by means of their stability and wide band gap tunability. Visible light induced photoelectrocatalytic water oxidation based on these material are challenging as they have large band gap energies. Herein, we report that MnO doping can activate wide band gap semiconductors like SnO2 towards visible light induced water oxidation. Rutile SnO2 nanoparticles (band gap 3.6eV), usually absorbing at UV region, was capable of harvesting visible light when doped with MnO thereby minimizing the energy requirement for photoelctrocatalytic water splitting. The system was characterized using UV-Vis, TEM and XPS. Photoelectrocatalytic activity was examined by LSV and CPE. The highly stable catalyst showed very good photoelectrocatalytic activity for the oxidation of water under alkaline condition with low overpotential of ∼370mV at 1.0mAcm-2.

Cerium(III) Complex Modified Gold Electrode: An Efficient Electrocatalyst for the Oxygen Evolution Reaction.

Exploring efficient and inexpensive electrocatalysts for the oxidation of water is of great importance for various electrochemical energy storage and conversion technologies. In the present study, a new water-soluble [Ce(III)(DMF) (HSO4)3] complex was synthesized and characterized by UV-vis, photoluminescence, and high-resolution X-ray photoelectron spectroscopy techniques. Owing to classic 5d → 4f transitions, an intense photoluminescence in the UV region was observed from the water-soluble [Ce(III)(DMF) (HSO4)3] complex. A stacking electrode was designed where self-assembled l-cysteine monolayer modified gold was immobilized with the synthesized cerium complex and was characterized by scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. The resulting electrode, i.e., [Ce(III)(DMF) (HSO4)3]-l-cysteine-Au stacks shows high electrocatalytic water oxidation behavior at an overpotential of η ≈ 0.34 V under neutral pH conditions. We also demonstrated a way where the overpotential is possible to decrease upon irradiation of UV light.