The mechanistically distinct and synergistic role of phosphite anions in hydrogen evolution nickel cations oxygen have been uncovered for active durable overall water splitting catalysis phosphite.

Water splitting, leading to hydrogen and oxygen in a process that mimics natural photosynthesis, is extremely important for devising sustainable solar energy conversion system. Development of earth-abundant, transition metal-based catalysts mimic the oxygen-evolving complex photosystem II, which involved oxidation water O2 during represents major challenge. Further, understanding exact mechanism, including elucidation role active metal-oxo intermediates (WO), critical development more...

Electrochemical splitting of water to oxygen and hydrogen using earth-abundant first-row transition metal-based catalysts is a promising approach for sustainable energy conversion. Herein, we present new convenient synthesis copper nitride (Cu3N) that acts as bifunctional electro(pre)catalyst evolution reaction (OER), (HER), overall electrolysis in alkaline media. Strikingly, the electrophoretically deposited Cu3N on nickel foam (NF) displayed extremely low overpotentials both OER HER, cell...

Abstract A highly active FeSe 2 electrocatalyst for durable overall water splitting was prepared from a molecular 2Fe‐2Se precursor. The as‐synthesized electrophoretically deposited on nickel foam and applied to the oxygen hydrogen evolution reactions (OER HER, respectively) in alkaline media. When used as an oxygen‐evolution electrode, low 245 mV overpotential achieved at current density of 10 mA cm −2 , representing outstanding catalytic activity stability because Fe(OH) /FeOOH sites...

Abstract Over the years, cobalt phosphates (amorphous or crystalline) have been projected as one of most significant and promising classes nonprecious catalysts studied exclusively for electrocatalytic photocatalytic oxygen evolution reaction (OER). However, their successful utilization hydrogen (HER) overall water‐splitting is rather unexplored. Herein, presented a crystalline phosphate, Co 3 (OH) 2 (HPO 4 ) , structurally related to mineral lazulite, an efficient precatalyst OER, HER,...

An Fe(V)(O) complex has been synthesized from equimolar solutions of (Et4N)2[Fe(III)(Cl)(biuret-amide)] and mCPBA in CH3CN at room temperature. The characterized by UV-vis, EPR, Mössbauer, HRMS shown to be capable oxidizing a series alkanes having C-H bond dissociation energies ranging 99.3 kcal mol(-1) (cyclohexane) 84.5 (cumene). Linearity the Bell-Evans-Polayni graph finding large kinetic isotope effect suggest that hydrogen abstraction is engaged rate-determining step.

A facile synthetic route to NiPt3@NiS heteronanostructures is reported, starting from a subsulfido bridged heterobimetallic nickel-platinum molecular precursor. Notably, the on nickel foam displayed merely an overpotential of 12 mV at -10 mA cm-2, which substantially lower than that Pt or NiS, synthesized through similar approach and represents most active hydrogen evolution reaction (HER) electrocatalysts yet reported in alkaline solutions. electrodes demonstrated unceasing HER stability...

Abstract The synthesis of structurally ordered non‐noble intermetallic cobalt stannide (CoSn 2 ) nanocrystals and their utilization for high‐performance electrocatalytic overall water‐splitting is presented. electronically beneficial properties the tetragonal CoSn exhibit a considerably low overpotential oxygen evolution reaction (OER) hydrogen (HER) on fluorine‐doped tin oxide (FTO) Ni foam (NF). Loss Sn from crystal lattices oxidation Co under strongly alkaline conditions furnishes highly...

The first β-diketiminato triphosphido diiron complex was synthesized as a versatile molecular single-source precursor for the production of functional FeP that acts powerful and durable bifunctional electrocatalyst water splitting.

An [FeIII(biuret-amide)] complex has been immobilized onto mesoporous silica nanoparticles via Cu(I) catalyzed azide–alkyne click chemistry. This hybrid material functions as an efficient peroxidase mimic and was successfully used for the quantitative determination of hydrogen peroxide glucose a one-pot colorimetric assay.

Abstract The synthesis of structurally ordered non‐noble intermetallic cobalt stannide (CoSn 2 ) nanocrystals and their utilization for high‐performance electrocatalytic overall water‐splitting is presented. electronically beneficial properties the tetragonal CoSn exhibit a considerably low overpotential oxygen evolution reaction (OER) hydrogen (HER) on fluorine‐doped tin oxide (FTO) Ni foam (NF). Loss Sn from crystal lattices oxidation Co under strongly alkaline conditions furnishes highly...

An Fe(III) complex of a biuret-amide based macrocyclic ligand that exhibits both excellent reactivity for the activation H2O2 and high stability, especially at low pH ionic strength, is reported.

[FeII(NCCH3)(NTB)](OTf)2 (NTB = tris(2-benzimidazoylmethyl)amine, OTf trifluoromethanesulfonate) was reacted with difluoro(phenyl)-λ3-iodane (PhIF2) in the presence of a variety saturated hydrocarbons, resulting oxidative fluorination hydrocarbons moderate-to-good yields. Kinetic and product analysis point towards hydrogen atom transfer oxidation prior to fluorine radical rebound form fluorinated product. The combined evidence supports formation formally FeIV(F)2 oxidant that performs...

Abstract The catalytic activity of the N ‐tailed (“biuret”) TAML (tetraamido macrocyclic ligand) activators [Fe{4‐XC 6 H 3 ‐1,2‐( COCMe 2 CO) NR}Cl] 2− ( ; atoms in boldface are coordinated to central iron atom; same nomenclature is used for compounds 1 and below), [X, R=H, Me a ); NO , b H, Ph c )] oxidative bleaching Orange II dye by O aqueous solution mechanistically compared with previously investigated activator CMe }OH ] − ) more aggressive analogue [Fe(Me C{CON(1,2‐C ‐4‐X) CO} )OH )....

Peroxidase, such as horseradish peroxidase (HRP), conjugated to antibodies are routinely used for the detection of proteins via an ELISA type assay in which a critical step is catalytic signal amplification by enzyme generate detectable signal. Synthesis functional mimics that display activity far exceeds native extremely important precise and accurate determination very low quantities (fM lower) necessary early clinical diagnosis. Despite great advancements, analyzing abundance...

Abstract A highly active FeSe 2 electrocatalyst for durable overall water splitting was prepared from a molecular 2Fe‐2Se precursor. The as‐synthesized electrophoretically deposited on nickel foam and applied to the oxygen hydrogen evolution reactions (OER HER, respectively) in alkaline media. When used as an oxygen‐evolution electrode, low 245 mV overpotential achieved at current density of 10 mA cm −2 , representing outstanding catalytic activity stability because Fe(OH) /FeOOH sites...

Nonheme iron complexes bearing tetradentate N-atom-donor ligands with cis labile sites show great promise for chemoselective aliphatic C–H hydroxylation. However, several challenges still limit their widespread application. We report a mechanism-guided development of peroxidase mimicking complex based on the bTAML macrocyclic ligand framework (Fe-bTAML: biuret-modified tetraamido ligand) as catalyst to perform selective oxidation unactivated 3° bonds unprecedented regioselectivity (3°:2°...

The presence of an FeV(O) species has been postulated as the active intermediate for oxidation both C–H and C═C bonds in Rieske dioxygenase family enzymes. Understanding reactivity these high valent iron–oxo intermediates, especially aqueous medium, would provide a better understanding enzymatic reaction mechanisms. formation complex at room temperature CH3CN mixture that contains up to 90% water using NaOCl oxidant is reported here. stability decreases with increasing concentration. We show...

We anticipate high-valent metal-fluoride species will be highly effective hydrogen atom transfer (HAT) oxidants because of the magnitude H-F bond (in product) that drives HAT oxidation. prepared a dimeric Fe

Abstract The formation and detailed spectroscopic characterization of the first biuret‐containing monoanionic superoxido‐Ni II intermediate [LNiO 2 ] − as Li salt [ ; L=MeN[C(=O)NAr) Ar=2,6‐iPr C 6 H 3 )] is reported. It results from oxidation corresponding [Li(thf) [LNi Br complex M with excess O in presence Et N. core shows an unprecedented nucleophilic reactivity oxidative deformylation aldehydes, stark contrast to electrophilic character previously reported neutral Nacnac‐containing 1 ,...

Catalytic signal amplification was used for the colorimetric detection of CN(-) in aqueous media by using enzyme catalase tandem with mesoporous silica nanoparticle based synthetic HRP mimic Fe-MSNs. Signal up to a maximum eight fold observed reporter "oxidized TMB" respect added ion.

Abstract Reactive oxygen species (ROS) containing sulfate and hydroxyl radicals can act as Fenton type reagents to remove organic contaminants from water. Here, a catalytic system silver metavanadate is reported for the activation of peroxodisulfate in an aqueous medium generate ROS, which further utilized efficient degradation water‐soluble pollutants such phenols, pesticides, antibiotics, dyes. Remarkably, complete carbon mineralization achieved form dioxide major product. In‐situ electron...

Abstract Die Niedertemperatursynthese von anorganischen Materialien und ihren Grenzflächen bietet zahlreiche Möglichkeiten für die Entwicklung Optimierung anorganischer in der heterogenen Katalyse, um eine nachhaltige chemische Energieumwandlung oder andere Anwendungen Energie einsparenden Bereichen zu ermöglichen. Verwendung geeigneter molekularer Vorstufen zur Synthese funktioneller Nanomaterialien ermöglicht Kontrolle über einheitliche Partikelgrößenverteilung Stöchiometrie im Hinblick...