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Patterning of BiVO4 Surfaces and Monitoring of Localized Catalytic Activity Using Scanning Photoelectrochemical Microscopy

There is a lot of interest in understanding localized catalytic activities at the micro and nanoscale and designing robust catalysts for photoelectrochemical oxidation of water to address the pressing energy and environmental challenges. Here, we demonstrate that scanning photoelectrochemical microscopy (SPECM) can be effectively employed as a novel technique (i) to modify a photocatalyst surface with an electrocatalyst layer in a matrix fashion and (ii) to monitor its localized activity toward the photoelectrochemical (PEC) water oxidation reaction. The three-dimensional SPECM image clearly shows that the loading of the FeOOH electrocatalyst on the BiVO4 semiconductor surface strongly affects its local PEC reaction activity. The optimal photoelectrodeposition time of FeOOH on the BiVO4 photocatalyst was found to be a?20 min when FeOOH was employed as the electrocatalyst. The electrocatalyst optimization process was conducted on a single photoanode electrode surface, making the optimization process efficient and reliable. The morphology of the formed photocatalyst/electrocatalyst hybrid, inclusive of its localized activity toward the water oxidation reaction, was simultaneously probed. A photoanode surface comprising CuWO4/BiVO4/FeOOH was further prepared in this study and investigated. It was found that the localized photoactivity truly reflects the activity of the local area, differs from region to region, and is contingent on the morphology of the surface. Moreover, the Pt UME is determined as an efficient probe to analyze the photoactivity of the PEC water splitting reaction. This work highlights the novel SPECM technique for enhancement and examination of the catalytic activity of the nanostructured materials.

Patterning of BiVO4 Surfaces and Monitoring of Localized Catalytic Activity Using Scanning Photoelectrochemical Microscopy

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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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Photoinduced charge transfer in short-distance ferrocenylsubphthalocyanine dyads

Two new ferrocenylsubphthalocyanine dyads with ferrocenylmethoxide (2) and ferrocenecarboxylate (3) substituents directly attached to the subphthalocyanine ligand via the axial position have been prepared and characterized using NMR, UV-vis, and magnetic circular dichroism (MCD) spectroscopies as well as X-ray crystallography. The redox properties of the ferrocenyl-containing dyads 2 and 3 were investigated using the cyclic voltammetry (CV) approach and compared to those of the parent subphthalocyanine 1. CV data reveal that the first reversible oxidation is ferrocene-centered, while the second oxidation and the first reduction are localized on the subphthalocyanine ligand. The electronic structures and nature of the optical bands observed in the UV-vis and MCD spectra of all target compounds were investigated by a density functional theory polarized continuum model (DFT-PCM) and time-dependent (TD)DFT-PCM approaches. It has been found that in both dyads the highest occupied molecular orbital (HOMO) to HOMO-2 are ferrocene-centered molecular orbitals, while HOMO-3 as well as lowest unoccupied molecular orbital (LUMO) and LUMO+1 are localized on the subphthalocyanine ligand. TDDFT-PCM data on complexes 1-3 are consistent with the experimental observations, which indicate the dominance of pi-pi* transitions in the UV-vis spectra of 1-3. The excited-state dynamics of the dyads 2 and 3 were investigated using time-correlated single photon counting, which indicates that fluorescence quenching is more efficient in dyad 3 compared to dyad 2. These fluorescence lifetime measurements were interpreted on the basis of DFT-PCM calculations.

Photoinduced charge transfer in short-distance ferrocenylsubphthalocyanine dyads

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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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The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2012

This is a review of papers published in the year 2012 that focus on the synthesis, reactivity, or properties of compounds containing a carbon-transition metal double or triple bond.

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2012

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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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Electron-Transfer Studies of Model Redox-Active Species (Cationic, Anionic, and Neutral) in Deep Eutectic Solvents

The redox potentials of electroactive species are significantly influenced by the solvation characteristics of the medium. This is manifested in the shift of half-peak potentials with the change in the solvent medium. There have been many approaches till date, both experimental and theoretical to understand the role of molecular solvents in the peak potentials of redox species. The electrochemical studies reported here are aimed at understanding the effect of deep eutectic solvents (DESs) which is distinct from conventional solvents in terms of highly concentrated ionic composition, on the half-peak potentials of some standard redox reactions. The redox species selected for this study are distinct either in terms of their charge [Fe(CN)64-/3-, Ru(NH3)62+/3+, and ferrocene methanol, FcMeOH0/+] or their hydrophilic/hydrophobic properties [methyl viologen and ferrocene]. The redox potentials are compared with the values obtained in the aqueous medium which is very well characterized in terms of solvent reorganization energy and free-energy changes. The cyclic voltammetric behavior of the redox species in DES is significantly different from that of aqueous medium. The diffusion coefficients of the redox species in DES measured by EIS and cyclic voltammetry showed significant deviations from that predicted by Stokes-Einstein equation, indicating the dominant effect of Coulombic interactions within the components of DES.

Electron-Transfer Studies of Model Redox-Active Species (Cationic, Anionic, and Neutral) in Deep Eutectic Solvents

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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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A novel side-chain ferrocene-containing polymer by combination of Cu(0)-mediated SET-LRP of acrylonitrile and post-modification

Well-defined side-chain ferrocene-containing polymers have been synthesized by post-modification of well-defined polyacrylonitrile (PAN). PAN prepared by Cu(0)-mediated single-electron transfer living radical polymerization was further modified using sodium azide and ammonium chloride (NH4Cl) to yield polymeric materials with vinyltetrazole units. Side-chain ferrocene-containing polymer was prepared by vinyltetrazole units and hydroxymethylferrocene after Mitsunobu reaction. FTIR, 1H NMR, UV?Vis spectroscopy and thermogravimetric analysis were used to identify the structure of the target product. After linked the ferrocene unit, the final polymer showed typical redox property?with?a?more negative?redox?potential (E1/2).

A novel side-chain ferrocene-containing polymer by combination of Cu(0)-mediated SET-LRP of acrylonitrile and post-modification

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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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The Reactivity of Ferrocene and Its Derivatives in the Reaction with Quinines

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.

The Reactivity of Ferrocene and Its Derivatives in the Reaction with Quinines

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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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Progress and recent advances in fabrication and utilization of hypoxanthine biosensors for meat and fish quality assessment: A review

This review provides an update on the research conducted on the fabrication and utilization of hypoxanthine (Hx) biosensors published over the past four decades. In particular, the review focuses on progress made in the development and use of Hx biosensors for the assessment of fish and meat quality which has dominated research in this area. The various fish and meat freshness indexes that have been proposed over this period are highlighted. Furthermore, recent developments and future advances in the use of screen-printed electrodes and nanomaterials for achieving improved performances for the reliable determination of Hx in fish and meat are discussed.

Progress and recent advances in fabrication and utilization of hypoxanthine biosensors for meat and fish quality assessment: A review

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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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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 ELECTROPHILIC SUBSTITUTION OF FERROCENE BY PROTONATED CARBONYL COMPOUNDS

The alpha-ferrocenylalkyl carbenium ions are formed from ferrocene and carbonyl compounds in strongly acidic media, in particular mixtures of fluorosulfuric acid and trichloroacetic acid.The alpha-ferrocenylalkyl carbenium ions are scavenged by nucleophiles or bases.The addition of nucleophiles produces the corresponding alpha-substituted ferrocenyl alkanes.Proton abstraction by base from the beta-position leads to the ferrocenylethene derivatives.Such electrophilic substitutions of ferrocene by carbonyl compounds, followed by suitable scavengeing of the alpha-ferrocenylalkyl carbenium ion, form the basis of one-pot syntheses of various ferrocene derivatives.

THE ELECTROPHILIC SUBSTITUTION OF FERROCENE BY PROTONATED CARBONYL COMPOUNDS

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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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alpha-ferrocenylalkylation of 1,5-disubstituted tetrazoles and certain transformations of reaction products

The reaction of alpha-hydroxyferrocenylalkyl derivatives and vinylferrocene with 1,5-disubstituted tetrazoles in methylene chloride-aqueous acid HX (X = BF4, ClO4) two-phase systems gives a mixture of 1,3,5- and 1,4,5-trisubstituted tetrazolium salts, the fraction of the 1,3,5-isomers prevailing. The synthesized salts are readily dealkylated under the action of bases to give the above starting compounds. Heating of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium and 3(4)-(ferrocenylmethylene)-2-methyl-1-phenyltetrazolium tetrafluoroborates in anhydrous methanol or ethanol in the presence of catalytic amounts of alkali gives rise to ferrocenylcarbinol ethers. Other nuclephiles (pyridine, triphenylphosphine, sodium thiocyanate, sodium p-toluenesulfinate, dibenzoylmethane) also react with the above tetrazolium salts, forming ferrocenylmethylation products. Heating of equimolar amounts of 3(4)-(ferrocenylmethylene)-1,5-pentamethylenetetrazolium or 3(4)- (ferrocenylmethylene)-2-methyl-1-phenyltetrazolium perchlorates with mercury(II) perchlorates in anhydrous ethanol results in mercuration of the starting tetrazolium salts, involving hydrogen substitution in the methylene or methyl groups bound to tetrazolium carbon atoms. The condensation of the same salts with p-N,N-(dimethylamino)nitrosobenzene, leading to azomethine formation, occurs under similar conditions.

alpha-ferrocenylalkylation of 1,5-disubstituted tetrazoles and certain transformations of reaction products

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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