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Metal-air batteries and fuel cells show a great deal of promise in advancing low-cost, high-energy-density charge storage solutions for sustainable energy applications. To improve the activities and stabilities of electrocatalysts for the critical oxygen reduction and evolution reactions (ORR and OER, respectively), a greater understanding is needed of the catalyst/carbon interactions and carbon stability. Herein, we report how LaNiO3 (LNO) supported on nitrogen-doped carbon nanotubes (N-CNT) made from a high-yield synthesis lowers the overpotential for both the OER and ORR markedly to enable a low bifunctional window of 0.81 V at only a 51 mug cm-2 mass loading. Furthermore, the addition of LNO to the N-CNTs improves the galvanostatic stability for the OER by almost 2 orders of magnitude. The nanoscale geometries of the perovskites and the CNTs enhance the number of metal-support and charge transfer interactions and thus the activity. We use rotating ring disk electrodes (RRDEs) combined with Tafel slope analysis and ICP-OES to quantitatively separate current contributions from the OER, carbon oxidation, and even anodic iron leaching from carbon nanotubes.

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Reference:
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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A suitable method for the synthesis of ferrocenyl(alkyl)imidazoles is proposed. The treatment of alpha-ferrocenylcarbinols with N,N?-carbonyldiimidazole affords the title compounds, are in more than 80% yields.

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Reference:
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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Binary Zr-Ti alloys spontaneously develop a tenacious and compact oxide layer when their fresh surface is exposed either to air or to aqueous environments. Electrochemical impedance spectroscopy (EIS) analysis of Zr-45Ti, Zr-25Ti, and Zr-5Ti exposed to simulated physiological solutions at 37 C evidences the formation of a non-sealing bilayer oxide film that accounts for the corrosion resistance of the materials. Unfortunately, these oxide layers may undergo breakdown and stable pitting corrosion regimes at anodic potentials within the range of those experienced in the human body under stress and surgical conditions. Improved corrosion resistance has been achieved by prior treatment of these alloys using thermal oxidation in air. EIS was employed to measure the corrosion resistance of the Zr-Ti alloys in simulated physiological solutions of a wide pH range (namely 3 ? pH ? 8) at 37 C, and the best results were obtained for the alloys pre-treated at 500 C. The formation of the passivating oxide layers in simulated physiological solution was monitored in situ using scanning electrochemical microscopy (SECM), finding a transition from an electrochemically active surface, characteristic of the bare metal, to the heterogeneous formation of oxide layers behaving as insulating surfaces towards electron transfer reactions.

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Reference:
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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The challenge in the C-C cross-coupling of secondary and primary alcohols using acceptorless dehydrogenation coupling (ADC) is the difficulty in accurately controlling product selectivities. Herein, we report a controlled approach to a diverse range of beta-alkylated secondary alcohols, alpha-alkylated ketones and alpha,beta-unsaturated ketones using the ADC methodology employing a Ni(ii) 4,6-dimethylpyrimidine-2-thiolate cluster catalyst under different reaction conditions. This catalyst could tolerate a wide range of substrates and exhibited a high activity for the annulation reaction of secondary alcohols with 2-aminobenzyl alcohols to yield quinolines. This work is an example of precise chemoselectivity control by careful choice of reaction conditions.

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Reference:
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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Antioxidants are widely found or used in food, pharmaceutical, and cosmetics industries; thus, rapid and sensitive detection of antioxidants is of great interest. The present work reports a simple and fast electrochemical method for direct analysis of antioxidants in fruit juices by modulating the permeability of mesochannels on the electrode surface. This goal was achieved by growing vertical silica mesochannel array (SMA) with a channel diameter of 2-3 nm on the indium tin oxide (ITO) electrode surface using the cylindrical micelles (CMs) as the template. As-prepared electrodes, designed as CM@SMA/ITO, are only permeable to lipophilic antioxidants, e.g., retinol, with the hydrophobic hydrocarbon cores of CMs. After excluding CMs from silica mesochannels, the ITO electrode modified with bare SMA, namely SMA/ITO, possesses a high density of silanol groups on the channel wall and thus is only permeable to hydrophilic antioxidants, such as ascorbic acid (AA). Two types of sensors allowed the selective analyses of retinol and AA in buffer solutions and demonstrated a wide linear range for retinol (1-60 muM) and AA (10-2000 muM), respectively, and a low detection limit (0.65 muM for retinol and 0.52 muM for AA). Moreover, the SMA/ITO electrode can selectively determine the concentration of AA in orange juice. The CM@SMA/ITO electrode can measure the sum activity of lipophilic antioxidants, such as retinol, alpha-tocopherol, and others possibly coexisting, in carrot juice. In addition, the ultrasmall mesochannels and CMs could effectively exclude the access of large substances, rendering an excellent antifouling and anti-interference ability for direct analysis of antioxidants in fruit juices without sample pretreatment. (Graph Presented).

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Reference:
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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Herein, we present a simple microelectrode preparation methodology consisting in coating a platinum wire or a carbon fiber with a thin insulating Parylene C film (e.g. 1-10 mum), to produce SECM probes with a small and constant probe RG (i.e. ratio between the radius of the insulating sheath and the radius of the active electrode area). After exposition of a fresh active electrode area by blade cutting, a disc shaped electrode is obtained thanks to a protective hot mounting wax layer that avoids Parylene C coating deformation and is easily removed with acetone. Stiffness and straightness of the probe can be tuned by modifying the Parylene C coating thickness and the length of the carbon fiber or platinum wire. This simple electrode preparation method is highly reproducible (c.a. > 90%). The prepared Parylene C coated microelectrodes were characterized by optical microscopy, cyclic voltammetry, scanning electrochemical microscopy (SECM) approach curves and finally applied to SECM imaging of Pt band structures in contact-less and contact mode.

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Reference:
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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The binding affinity of calix[6]arene hexasulfonate hosts for ferrocene or cobaltocenium guests is highly dependent on the extent of intramolecular hydrogen bonding in the lower rim of the calixarene.

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Reference:
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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In situ scanning electrochemical microscopy (SECM) and scanning tunneling microscopy (STM) assisted scanning reference electrode technique (SRET) were applied for the first time to study the interaction of thiosulfate with Alloy 800 surfaces in aqueous chloride solutions. Electrochemical impedance spectroscopy (EIS) and scanning electron microscope (SEM) were also performed to understand the interaction mechanism. The results showed that the effect of 0.075 mol/L thiosulfate in 0.6 mol/L chloride solutions strongly depended on the potential. There was no aggressive effect at the corrosion potential where the passive layer was intact, but a combined effect was observed with the presence of chloride ions at high potential where the passive layer was broken down.

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Reference:
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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Hydroalumination reaction was effectively carried out on ferrocenylnitrile in the synthesis of imidoalane cluster [HAlNCH2C5H 4FeCp]6 (3). Compound 3 exhibits a reversible electrochemical behavior. In the presence of ferrocenylmethanol, meta thesis reactions were carried out on [HAlNCH2(C4H 3S)]6 (4) and [HAlNCH2Ph]6 (5) in the synthesis of [CpFeC5H4CH2OAlNCH 2(C4H3S)]6 (6) and [CpFeC 5H4CH2OAlNCH2Ph]6 (7). The ferrocenylmethoxide groups present in these two compounds show a single reversible oxidation wave, which suggests their electrochemical equivalence. Electrochemical studies were also carried out on the carbaalane [(AlH) 2(FcCCAl)4(AlNMe3)2(CCH 2Ph)6] (9), which exhibited a considerably broadened wave with shoulders preceding the main anodic and cathodic peak, and it can be assigned to weak electronic interactions between the individual ferrocenyl sites.

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Reference:
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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The reactivity of ferrocene derivatives with respect to p-quinones in acid media has been studied. A tentative mechanism of oxidation of ferrocene with p-qionone in acid media including two-step reduction of p-quinone to hydroquinone is proposed.

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Reference:
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