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Oxygen Reduction at Carbon-Supported Lanthanides: TheRole of the B-Site

The kinetics of the oxygen reduction reaction (ORR) at carbon-supported transition-metal oxides in alkaline solutions is systematically investigated as a function of the nature of the B-site. The study is focused on LaBO3 (B=Cr, Co, Fe, Mn and Ni) nanoparticles synthesized by using an ionic-liquid route, offering fine control over phase purity and composition. Activity towards the ORR was compared with the commercial Pt/Etek catalyst. Detailed electrochemical analysis employing a rotating ring-disk electrode provides conclusive evidence that the carbon support plays an important contribution in the faradaic responses. Decoupling the contribution of the carbon support uncovers that the reactivity of LaMnO3 towards the four-electron ORR pathway is orders of magnitude higher than that for the other lanthanides. We rationalize these observations in terms of changes in the redox state at the B-site close to the formal oxygen reduction potential.

Oxygen Reduction at Carbon-Supported Lanthanides: TheRole of the B-Site

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Suppressed photoelectrochemistry at carbon-surface-modified mesoporous TiO2 films

Cellulose nano-whiskers or nanocrystals are used as a carbon source in a vacuum graphitisation process to surface-modify nano-TiO2 and influence its photoreactivity. In sharp contrast to bulk carbon-modified TiO2 materials, introducing cellulose in a controlled way, i.e., a layer-by-layer deposition process, allows thin film materials to be created with low graphite content, but with strongly suppressed responses to light. The effect is explained by highly effective surface recombination and demonstrated for the I3-/I- redox system in acetonitrile and for the photo-oxidation of acetate in aqueous media.

Suppressed photoelectrochemistry at carbon-surface-modified mesoporous TiO2 films

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Stochastic amperometric fluctuations as a probe for dynamic adsorption in nanofluidic electrochemical systems

Adsorption of analyte molecules is ubiquitous in nanofluidic channels due to their large surface-to-volume ratios. It is also difficult to quantify due to the nanometric scale of these channels. We propose a simple method to probe dynamic adsorption at electrodes that are embedded in nanofluidic channels or which enclose nanoscopic volumes. The amperometric method relies on measuring the amplitude of the fluctuations of the redox cycling current that arise when the channel is diffusively coupled to a bulk reservoir. We demonstrate the versatility of this new method by quantifying adsorption for several redox couples, investigating the dependence of adsorption on the electrode potential and studying the effect of functionalizing the electrodes with self-assembled monolayers of organothiol molecules bearing polar end groups. These self-assembled monolayer coatings are shown to significantly reduce the adsorption of the molecules on to the electrodes. The detection method is not limited to electrodes in nanochannels and can be easily extended to redox cycling systems that enclose very small volumes, in particular scanning electrochemical microscopy with nanoelectrodes. It thus opens the way for imaging spatial heterogeneity with respect to adsorption, as well as rational design of interfaces for redox cycling based sensors.

Stochastic amperometric fluctuations as a probe for dynamic adsorption in nanofluidic electrochemical systems

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Addition of redox additive to ionic liquid electrolyte for high-performance electrochemical capacitors of n-doped graphene aerogel

To enhance the specific energy of electrochemical capacitors, several methods have been introduced including complex electrode modification as well as asymmetric cell development. Herein, an alternative approach to enhance both specific energy and power of N-doped reduced graphene oxide aerogel electrochemical capacitor via the introduction of hybrid redox electrolyte is proposed. The electrochemical properties of the hybrid electrolyte composing of 1-butyl-1-methylpyrrolidinium dicyanamide ionic liquid with 100mMferrocenemethanol redox additive were studied via cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. The combination between a unique nanostructure of N-doped reduced graphene oxide aerogel and novel hybrid electrolyte results in an excellent specific capacitance and specific energy of 112.1 F g-1 and 34.2 Wh kg-1, respectively, as compared to 76.7 F g-1 and 23.5 Wh kg-1 of the neat 1-butyl-1-methylpyrrolidinium dicyanamide electrolyte. The remarkable improvements can be explained by the emerging of the Faradaic-redox activity of the ferrocene methanol at the electrode-electrolyte interface. This simple approach could demonstrate another feasible route to improve the performance of ionic liquid-based electrochemical capacitors.

Addition of redox additive to ionic liquid electrolyte for high-performance electrochemical capacitors of n-doped graphene aerogel

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Graphene in combination with cucurbit[n]urils as electrode modifiers for electroanalytical biomolecules sensing

Cucurbit[n]urils have been supported on graphene to develop sensitive and selective electrodes. The electrochemical response of modified electrodes containing graphene or graphene plus cucurbiturils has been studied for three probe molecules including hydroxymethylferrocene, ferrocyanide and methylviologen. It was found that the properties of these modified electrodes are derived from an increase in electron mobility and catalytic activity imparted by graphene and the selective complexation and molecular recognition due to cucurbit[n]urils. These properties of the graphene/cucurbit[n]urils modified electrodes have been applied for the electrochemical detection of relevant biomolecules as tryptophan at 0.69¡Á10-7 M concentration.

Graphene in combination with cucurbit[n]urils as electrode modifiers for electroanalytical biomolecules sensing

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Development of a novel multifunctional N,P ligand for highly enantioselective palladium-catalyzed asymmetric allylic etherification of alcohols and silanols

CycloN2P2-Phos! The use of the multidentate phosphine, CycloN2P2-Phos (see graphic), which contains four heteroatoms (two nitrogen and two phosphorus atoms), in the palladium-catalyzed asymmetric allylic etherification (AAE) of alcohols and silanols leads to excellent levels of enantioselectivity (up to 99 %ee). Copyright

Development of a novel multifunctional N,P ligand for highly enantioselective palladium-catalyzed asymmetric allylic etherification of alcohols and silanols

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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We¡¯ll also look at important developments in the pharmaceutical industry because understanding organic chemistry is important in understanding health, medicine, the role of 1273-86-5, and how the biochemistry of the body works.Formula: C11H3FeO

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Conformational analysis of ferrocene-containing alcohols. A density functional study of weak OH…Fe interactions

Optimized geometries and vOH stretching frequencies are reported for a set of monosubstituted ferrocenes, Fe(C5H5)(C 5H4R) [R = (CH2)nOH (n = 1-4), CH(Me)OH, CH(tBu)OH], at the BP86 level of density functional theory. In addition, NMR chemical shifts have been computed at the GIAO-B3LYP level. In all species studied, the most stable conformer is characterized by an OH…Fe moiety with Fe…H distances in the region between 2.61 and 2.95 A, followed by conformers with OH…pi interactions involving the C(ipso) atoms of the cyclopentadienyl ring. According to population and topological (Bader) analyses of the electron density, these conformers are stabilized by weak electrostatic interactions, rather than by true intramolecular hydrogen bonds. The VOH stretching frequencies are a very sensitive probe for the OH…Fe interaction, and the observed red-shift of this band relative to isomers with “free” OH bonds, which can exceed 100 cm-1, is well reproduced computationally. When other H-bond acceptors are present, the intramolecular OH…Fe interaction cannot compete with intermolecular H-bond formation, as has been explicitly shown in a Car-Parrinello molecular dynamics (CPMD) simulation of Fe(C5H5)-(C 5H4CH2OH) in water. Compared to these unconstrained ferrocene-containing alcohols, somewhat stronger OH…Fe interactions can be present in ansa derivatives, e.g., in a [2]ferrocenophane derivative with a CH2CH2OH group, for which a bond path between Fe and the alcoholic H atom is found.

Conformational analysis of ferrocene-containing alcohols. A density functional study of weak OH…Fe interactions

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Voltammetric determination of diffusion coefficients in polymer membranes

The diffusion-controlled transport of ions and molecules through polymer membranes utilized in chemical and biosensors is often the key factor determining the response characteristics of these sensors. In this paper, a simple voltammetric method is described for the determination of diffusion coefficients of redox molecules in resistive polymer membranes using a planar electrochemical cell (PEC) with a 5 mum radius carbon fiber as working electrode. In the proposed method, the diffusion coefficients are assessed from the scan rate dependence of the peak (or limiting) currents in linear sweep or cyclic voltammograms. The accuracy of the method is estimated through simulations using the method of Nicholson and Shain describing the quantitative relationship between the measured peak current (ip) and the square root of the scan rate (v1/2). The proposed method has been used for measuring the diffusion coefficients of ferrocene derivatives in highly resistive aqueous solutions, organic solvents, plasticizers, and plasticized PVC membranes. The measured diffusion coefficients are in agreement with theoretical models and previously reported values.

Voltammetric determination of diffusion coefficients in polymer membranes

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Scanning electrochemical microscopy for the investigation of localized degradation processes in coated metals: Effect of oxygen

The effect of oxygen content on the corrosion reactions inside a holiday in a polymer-coated metal substrate was studied by SECM without adding a redox mediator. The system was mild steel coated by polyurethane in KCl. By selecting different values for the potential applied to the ultramicroelectrode tip, local concentrations of species involved in the degradation process are monitored, namely Fe(II) ions, hydrogen peroxide and oxygen. The results show a variation in both the shape and the magnitude of the scan lines measured over the holiday. A critical oxygen concentration was found below which the corrosion reaction is not observed.

Scanning electrochemical microscopy for the investigation of localized degradation processes in coated metals: Effect of oxygen

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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CAN catalysis and click chemistry routes in the synthesis of carborane-containing ferrocenes

CAN-catalyzed reactions between alpha-ferrocenyl ethanol or ferrocenyl methanol and S-, N- and O-carborane nucleophiles are reported. This approach is an efficient and simple procedure for the preparation of carborane derivatives containing ferrocenyl units. Energy and geometry optimizations of some carboranylthio-, carboranylamino- and carboranyloxy-substituted ferrocenes have been calculated using the density functional theory. A series of new ferrocene-containing carborane 1,2,3-triazoles have been synthesized in good yields through a facile copper-mediated 1,3-dipolar cycloaddition reactions of alkynyl ferrocenes with [(o-carboran-1-yl)methyl]azide. Molecular structure of carborane-substituted ferrocenyl triazole was established by single crystal X-ray diffraction study. Representative examples of all ferrocenyl carboranes prepared were characterized by IR, 1H and 11B NMR spectroscopy.

CAN catalysis and click chemistry routes in the synthesis of carborane-containing ferrocenes

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion