Redox Chemistry (redox + chemistry)

Distribution by Scientific Domains


Selected Abstracts


ChemInform Abstract: Topotactic Redox Chemistry of NaFeAs in Water and Air and Superconducting Behavior with Stoichiometry Change.

CHEMINFORM, Issue 37 2010
Iliya Todorov
Abstract The redox chemistry and transformations of NaFeAs in water and air are characterized by single crystal and powder XRD, magnetization measurements, TEM, and Moessbauer spectroscopy. [source]


ChemInform Abstract: Fe(VI) Catalyzed Manganese Redox Chemistry: Permanganate and Super-Iron Alkaline Batteries.

CHEMINFORM, Issue 6 2002
Stuart Licht
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source]


Diboryl and Diboranyl Porphyrin Complexes: Synthesis, Structural Motifs, and Redox Chemistry: Diborenyl Porphyrin or Diboranyl Isophlorin?

CHEMISTRY - A EUROPEAN JOURNAL, Issue 21 2007
Andre Weiss Dr.
Abstract The syntheses of diboryl porphyrin complexes [(BX2)2(ttp)] (ttp: dianion of tetra- p -tolylporphyrin) and the BB single-bond diboranyl complexes [(BX)2(ttp)] (X=F, Cl, Br, I) are given. The former are prepared from the reactions of BX3 (X=F, Cl) with [Li2(ttp)] and the latter from B2Cl4 (X=Cl), the reaction of SbF3 with [(BCl)2(ttp)] (for X=F), and, in the cases of X=Br or I, in a remarkable reductive coupling reaction resulting directly from the reaction of BBr3 or BI3 with [Li2(ttp)]. Density functional theory (DFT) calculations on the thermochemical parameters for the reductive coupling reactions (and those calculated for related dipyrromethene complexes) indicate that a combination of the reducing ability of bromide and iodide ions combined with the constrained environment of the porphyrin ligand contribute to the driving force. The reductive coupling is also observed in the reaction of [(BCl2)2(ttp)] with nBuLi to give [(BnBu)2(ttp)], which was characterised crystallographically. The reaction of [(BCl)2(ttp)] with catechol gives a boron catecholato porphyrin complex, [B2(O2C6H4)(ttp)]. Chloride abstraction from [(BCl)2(ttp)] gives the planar dication [B2(ttp)]2+, whereas chemical reduction of [(BCl)2(ttp)] by using magnesium anthracenide gives a neutral complex, [B2(ttp)], in which the TTP ligand has been reduced by two electrons to give an unusual example of an isophlorin complex. The cationic and neutral complexes [B2(ttp)]2+ and [B2(ttp)] were characterised through a combination of spectroscopic data that is supported by DFT calculations on the porphine analogues. [source]


A Dual Electrochrome of Poly-(3,4-Ethylenedioxythiophene) Doped by N,N,-Bis(3-sulfonatopropyl)-4-4,-bipyridinium,Redox Chemistry and Electrochromism in Flexible Devices

CHEMSUSCHEM CHEMISTRY AND SUSTAINABILITY, ENERGY & MATERIALS, Issue 1 2010
Shweta Bhandari
Abstract An electrochromic zwitterionic viologen, N,N,-bis(3-sulfonatopropyl)-4-4,-bipyridinium, has been used for the first time for doping poly (3,4-ethylenedioxythiopene) (PEDOT) films during electropolymerization. Slow and fast diffusional rates for the monomer at deposition potentials of +1.2 and +1.8,V, respectively yielded the viologen-doped PEDOT films with granular morphology and with dendrite-like shapes. The dual electrochrome formed at +1.8,V, showed enhanced coloration efficiency, larger electrochemical charge storage capacity, and superior redox activity in comparison to its analogue grown at +1.2,V, thus demonstrating the role of dendritic shapes in amplifying electrochromism. Flexible electrochromic devices fabricated with the viologen-doped PEDOT film grown at +1.8,V and Prussian blue with an ionic liquid-based gel electrolyte film showed reversible coloration between pale and dark purple with maximum coloration efficiency of 187,cm2,C,1 at ,=693,nm. The diffusional impedance parameters and switching kinetics of the device showed the suitability of this dual electrochrome formed as a single layer for practical electrochromic cells. [source]


Mass-independent fractionation of sulfur isotopes in sulfides from the pre-3770 Ma Isua Supracrustal Belt, West Greenland

GEOBIOLOGY, Issue 4 2006
D. PAPINEAU
ABSTRACT Redox chemistry of the coupled atmosphere,hydrosphere system has coevolved with the biosphere, from global anoxia in the Archean to an oxygenated Proterozoic surface environment. However, to trace these changes to the very beginning of the rock record presents special challenges. All known Eoarchean (c. 3850,3600 Ma) volcanosedimentary successions (i.e. supracrustal rocks) are restricted to high-grade gneissic terranes that seldom preserve original sedimentary structures and lack primary organic biomarkers. Although complicated by metamorphic overprinting, sulfur isotopes from Archean supracrustal rocks have the potential to preserve signatures of both atmospheric chemistry and metabolic fractionation from the original sediments. We present a synthesis of multiple sulfur isotope measurements (32S, 33S and 34S) performed on sulfides from amphibolite facies banded iron-formations (BIFs) and ferruginous garnet-biotite (metapelitic) schists from the pre-3770 Ma Isua Supracrustal Belt (ISB) in West Greenland. Because these data come from some of the oldest rocks of interpretable marine sedimentary origin, they provide the opportunity to (i) explore for possible biosignatures of sulfur metabolisms in early life; (ii) assess changes in atmospheric redox chemistry from ,3.8 Ga; and (iii) lay the groundwork to elucidate sulfur biogeochemical cycles on the early Earth. We find that sulfur isotope results from Isua do not unambiguously indicate microbially induced sulfur isotopic fractionation at that time. A significantly expanded data set of ,33S analyses for Isua dictates that the atmosphere was devoid of free oxygen at time of deposition and also shows that the effects of post-depositional metamorphic remobilization and/or dilution can be traced in mass-independently fractionated sulfur isotopes. [source]


Iron Absorption: Biochemical and Molecular Insights into the Importance of Iron Species for Intestinal Uptake

BASIC AND CLINICAL PHARMACOLOGY & TOXICOLOGY, Issue 3 2002
Piero Cremonesi
Redox chemistry of iron is particularly important in iron metabolism, both as a potential source of toxic intermediates and as an essential requirement for efficient iron transport. The initial step in iron absorption (uptake from lumen to mucosa) is particularly important and several pathways involving Fe(III) reduction or transport and Fe(II) transport have been identified. Novel genes associated with iron uptake include Dcytb, a putative iron-regulated reductase and DMT1, a Fe(II) carrier in the brush border membrane. Other mechanisms may also operate, however. We review the recent findings and apply this to understanding the absorption of Fe(III) pharmaceuticals. [source]


Electrochemistry of Nucleic Acids at Solid Electrodes and Its Applications

ELECTROANALYSIS, Issue 15 2004
Patricia de-los-Santos-lvarez
Abstract The knowledge of the redox chemistry of nucleic acids (NA) is of paramount importance in cancer and aging research. Charge migration through DNA is also involved in biologically relevant functions such as DNA damage and repair. In the first part of this article the main aspects of the electrochemistry of nucleic acids at solid electrodes are revised, including redox processes, photoelectroactivity and electrical conductivity. In the second part, an overview of its applications is presented. Methods for electrochemical detection of NA, NA-based biosensors for detection of nonnucleic acid molecules, studies on the nature and dynamics of interactions and structural conformations of NA, are some applications that take advantage of NA electrochemistry at solid electrodes. [source]


The Influence of Doping Levels and Surface Termination on the Electrochemistry of Polycrystalline Diamond

ELECTROANALYSIS, Issue 6 2004
Matthew
Abstract The influence of surface chemistry and boron doping density on the redox chemistry of Fe(CN) at CVD polycrystalline diamond electrodes is considered. It is demonstrated that for this couple both the doping density and the surface chemistry are important in determining the rate of charge transfer at the electrode/electrolyte interface. For hydrogen terminated CVD diamond metallic electrochemical behavior is always observed, even at boron doping densities as low as 71018,cm,3. In contrast, the electrochemical behavior of oxygen terminated CVD diamond varies with doping density, a metallic response being observed at high doping density and semiconductor behavior at low doping density. It is shown that the results attained may be explained by a surface state mediated charge transfer mechanism, thus demonstrating the importance of controlling surface chemistry in electroanalytical applications of diamond. [source]


Copper-Azide-Thioarylazoimidazoles , Structure, Spectra, Redox Properties, Magnetism and Theoretical Interpretation

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2010
Prasenjit Bhunia
Abstract Azido-copper(II) and -copper(I) complexes of 1-alkyl-2-[(o -thioalkyl)phenylazo]imidazole (SRaaiNR,) have been prepared and studied. Complex 2 [Cu(SRaaiNR,)(,1,1 -N3)(N3)]2 dimerises via end-to-end (,1,3)-N3 to form a tetrameric structure. Azido-copper(I) complexes of the ligands are obtained as MeOH-bridged dimers, [Cu(SRaaiNR,)(N3)(,-OHMe)]2 (3). The electronic spectra suggest that a small reorganisation energy (0.08 eV) is associated with the change in electronic configuration, structure and oxidation state from CuII to CuI. Redox interconversion, CuII , CuI, [Cu(SMeaaiNMe)(,-N3)(N3)]2 (2a) , [Cu(SMeaaiNMe)(N3)(,-OHCH3)]2 (3a), has been performed in one case. The tetranuclear complex shows ferromagnetic and antiferromagnetic interactions. The spectra, redox chemistry and magnetism are explained by DFT studies. [source]


Dinuclear Manganese and Cobalt Complexes with Cyclic Polyoxovanadate Ligands: Synthesis and Characterization of [Mn2V10O30]6, and [Co2(H2O)2V10O30]6,

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 34 2009
Shinnosuke Inami
Abstract An all-inorganic complex, [Mn2{(VO3)5}2]6, (1), was synthesized, and the structure determination reveals a dinuclear manganese complex coordinated by two cyclic pentavanadate ligands. The cyclic pentavanadate units sandwich the edge-sharing octahedral dimanganese core through coordination of the oxido group of the pentavanadate. A dinuclear cobalt complex with a cyclic decavanadate, [Co2(OH2)2(VO3)10]6, (2), was also synthesized. The structure analysis reveals a dinuclear cobalt complex with a macrocyclic decavanadate, which is composed of 10 VO4 units joined by the vertex sharings. The CoO6 octahedrons are edge-shared, with each cobalt octahedron coordinated to five oxido groups from the decavanadate. The remaining site is occupied by water. The coordinated water molecules are supported with hydrogen bonds in two directions. Complex 2 in acetonitrile shows no reactivity with dioxygen even at low temperature, and the cyclic voltammogram of 2 shows no redox chemistry in acetonitrile. Complex 2 exhibits chromism by water exposure both in the solid state and in acetonitrile. Complex 2 is green,yellow in color, and the addition of water causes the complex to turn brown. After heating the sample, it returns to its original color in a reversible manner. The EXAFS data in acetonitrile is also reported and is consistent with the solid-state structure. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]


Self-Assembly, Structure and Solution Dynamics of Tetranuclear Zn2+ Hydrazone [22] Grid-Type Complexes

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2006
Mihail Barboiu
Abstract We describe the self-assembly processes as well as the structural and physico-chemical properties of [22]Zn2+4 grid complexes involving the bis-tridentate ligands 7,12, based on bis(hydrazone)pyrimidine complexation subunits and octahedrally coordinated Zn2+ ions. The NMR spectroscopic data and the X-ray crystal structure results indicate that in solution and in the solid state the complexes 13,18 adopt a very compact arrangement providing stable [22] hydrazone-grid arrays. The ,,, stacking between the phenyl ring and the hydrazone units of the perpendicular ligands in the complexes induces a perfect orthogonal arrangement suitable for applications in self-organized metallosupramolecular systems. Zinc complexes provide an opportunity to study the acid,base chemistry without the added effects due to paramagnetism or redox chemistry. The intermediate protonated grids undergo relatively rapid proton exchange on the NMR timescale, the presence of a sharp pyrimidine proton resonance suggesting that there is significant delocalization of the negative charge along the backbone of the ligand. Rotation of the phenyl ring is observed. It involves probably a mechanism in which one of the ligands partially dissociates allowing the initially intercalated phenyl group to rotate, before recoordination of the terminal pyridine. ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]


Off the Back or on the Side: Comparison of meso and 2-Substituted Donor-Acceptor Difluoroborondipyrromethene (Bodipy) Dyads

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2010
Andrew C. Benniston
Abstract The preparation of several difluoroborondipyrromethene (Bodipy) dyads is described incorporating covalently attached hydroquinone/quinone groups at the 2-position (BD-SHQ, BD-SQ, BD-SPHQ, BD-SPQ). The compounds, currently under investigation as chemical sensors for reactive oxygen species, show various levels of fluorescence depending on the oxidation state of the appended group. The 19F NMR spectrum for BD-SHQ in CDCl3 at room temperature reveals the two fluorines are inequivalent on the NMR timescale. In contrast, the 19F NMR spectrum for the counterpart quinone compound, BD-SQ, is consistent with two equivalent fluorine atoms. The two results are interpreted as the quinone is free to rotate around the connector bond, whereas this motion is restricted for the hydroquinone group and makes the fluorines chemically inequivalent. Cyclic voltammograms recorded for all derivatives in CH2Cl2 electrolyte solution are consistent with typical Bodipy-based redox chemistry; the potentials of which depend on factors such as presence of the phenylene spacer and oxidation state of the appended group. A comparison of the electrochemical behaviour with the counterpart meso derivatives reveals some interesting trends which are associated with the location of the HOMO/LUMOs. The absorption profiles for the compounds in CH3CN are again consistent with Bodipy-based derivatives, though there are some subtle differences in the band-shapes of the closely-coupled systems. In particular, the absorption spectra for the dyad, BD-SQ, in a wide range of solvents are appreciably broader than for BD-SHQ. Femtosecond transient absorption spectroscopy performed on the hydroquinone derivatives, BD-SHQ and its meso analogue is interpreted as electron transfer occurs from the hydroquinone unit to the first-excited singlet (S1) state of the Bodipy center, followed by ultrafast charge recombination to reinstate the ground state. The coupling of OH vibrations to the return electron transfer process is invoked to explain the lack of clear identification of the charge-separated state in the transient records. [source]


Mass-independent fractionation of sulfur isotopes in sulfides from the pre-3770 Ma Isua Supracrustal Belt, West Greenland

GEOBIOLOGY, Issue 4 2006
D. PAPINEAU
ABSTRACT Redox chemistry of the coupled atmosphere,hydrosphere system has coevolved with the biosphere, from global anoxia in the Archean to an oxygenated Proterozoic surface environment. However, to trace these changes to the very beginning of the rock record presents special challenges. All known Eoarchean (c. 3850,3600 Ma) volcanosedimentary successions (i.e. supracrustal rocks) are restricted to high-grade gneissic terranes that seldom preserve original sedimentary structures and lack primary organic biomarkers. Although complicated by metamorphic overprinting, sulfur isotopes from Archean supracrustal rocks have the potential to preserve signatures of both atmospheric chemistry and metabolic fractionation from the original sediments. We present a synthesis of multiple sulfur isotope measurements (32S, 33S and 34S) performed on sulfides from amphibolite facies banded iron-formations (BIFs) and ferruginous garnet-biotite (metapelitic) schists from the pre-3770 Ma Isua Supracrustal Belt (ISB) in West Greenland. Because these data come from some of the oldest rocks of interpretable marine sedimentary origin, they provide the opportunity to (i) explore for possible biosignatures of sulfur metabolisms in early life; (ii) assess changes in atmospheric redox chemistry from ,3.8 Ga; and (iii) lay the groundwork to elucidate sulfur biogeochemical cycles on the early Earth. We find that sulfur isotope results from Isua do not unambiguously indicate microbially induced sulfur isotopic fractionation at that time. A significantly expanded data set of ,33S analyses for Isua dictates that the atmosphere was devoid of free oxygen at time of deposition and also shows that the effects of post-depositional metamorphic remobilization and/or dilution can be traced in mass-independently fractionated sulfur isotopes. [source]


Synthesis, structure, reactions, and photoelectron spectra of new mixed sulfur-, selenium- or tellurium and silicon- or tin-containing heterocycles

HETEROATOM CHEMISTRY, Issue 5 2007
Eric Block
More than 40 new 4- to 12-membered ring heterocycles containing various combinations of Group 14 elements (Si and Sn) and Group 16 elements (S, Se, and Te) have been synthesized and fully characterized. Synthesis of these small-ring as well as medium-ring (mesocyclic) heterocycles from ,, ,-dihalides was facilitated by the presence of gem-dialkylsilyl and gem-dialkylstannyl groups in the precursors. Solid-state conformations of the new ring systems have been determined by X-ray crystallography. Oxidation of mixed S(Se, Te)/Si eight-membered ring mesocycles as well as 1,5-dithia-, 1,5-diselena-, and 1,5-ditelluracyclooctane with NOPF6 gave dications, which can be characterized by NMR. On treatment with nucleophiles, mesocyclic dications or the corresponding radical cations underwent ring contraction to give five- or six-membered ring heterocycles. The ionization energies of the above conformationally constrained ,-disilanyl sulfides and selenides were determined by photoelectron spectroscopy. These ionization energies reflect substantial (0.53--0.75 eV) orbital destabilizations. The basis for these destabilizations was investigated by theoretical calculations, which reveal geometry-dependent interaction between sulfur or selenium lone pair orbitals and ,-orbitals, especially Si,Si ,-orbitals. These results suggest facile redox chemistry for these compounds and significantly extend the concept of ,-stabilization of electron-deficient centers. 2007 Wiley Periodicals, Inc. 18:509,515, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20333 [source]


Ferrocene Redox Controlled Reversible Immobilization of Ruthenium Carbene in Ionic Liquid: A Versatile Catalyst for Ring-Closing Metathesis

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009
Guiyan Liu
Abstract A ferrocene-tagged ruthenium carbene 15 that can be reversibly immobilized in an ionic liquid (IL) via the controlled oxidation and reduction of a ferrocene tag was prepared. This offers a new strategy which uses redox chemistry to control immobilization and to recycle both the catalyst and the IL. In this experiment, 11 recycles were performed for the ring-closing metathesis (RCM) of a substrate using 16 as the catalyst in an ionic liquid (IL). More importantly, after the reaction was completed, the ruthenium catalyst was easily separated from the supporting IL by just adding decamethylferrocene (DMFc) to reduce the cationic ferrocene and then extracting it with benzene. Thus, this recycle system offers an easy way to recycle both the ruthenium catalyst and the IL. [source]


The effect of the sixth sulfur ligand in the catalytic mechanism of periplasmic nitrate reductase

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 15 2009
N. M. F. S. A. Cerqueira
Abstract The catalytic mechanism of nitrate reduction by periplasmic nitrate reductases has been investigated using theoretical and computational means. We have found that the nitrate molecule binds to the active site with the Mo ion in the +6 oxidation state. Electron transfer to the active site occurs only in the proton-electron transfer stage, where the MoV species plays an important role in catalysis. The presence of the sulfur atom in the molybdenum coordination sphere creates a pseudo-dithiolene ligand that protects it from any direct attack from the solvent. Upon the nitrate binding there is a conformational rearrangement of this ring that allows the direct contact of the nitrate with MoVI ion. This rearrangement is stabilized by the conserved methionines Met141 and Met308. The reduction of nitrate into nitrite occurs in the second step of the mechanism where the two dimethyl-dithiolene ligands have a key role in spreading the excess of negative charge near the Mo atom to make it available for the chemical reaction. The reaction involves the oxidation of the sulfur atoms and not of the molybdenum as previously suggested. The mechanism involves a molybdenum and sulfur-based redox chemistry instead of the currently accepted redox chemistry based only on the Mo ion. The second part of the mechanism involves two protonation steps that are promoted by the presence of MoV species. MoVI intermediates might also be present in this stage depending on the availability of protons and electrons. Once the water molecule is generated only the MoVI species allow water molecule dissociation, and, the concomitant enzymatic turnover. 2009 Wiley Periodicals, Inc. J Comput Chem, 2009 [source]


Crystallization and preliminary X-ray analysis of the small subunit (R2F) of native ribonucleotide reductase from Corynebacterium ammoniagenes

ACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 9 2009
Hideaki Ogata
Ribonucleotide reduction, the unique step in DNA-precursor biosynthesis, involves radical-dependent redox chemistry and diverse metallo-cofactors. The metallo-cofactor (R2F) encoded by the nrdF (nucleotide reduction) gene in Corynebacterium ammoniagenes ATCC 6872 was isolated after homologous expression and a new crystal form of ribonucleotide reductase R2F was obtained. R2F was crystallized at 277,K using the vapour-diffusion method with PEG as the precipitating agent. A data set was collected to 1.36, resolution from a single crystal at 100,K using synchrotron radiation. The crystal belonged to space group C2, with unit-cell parameters a = 96.21, b = 87.68, c = 83.25,, , = 99.29. The crystal contained two molecules per asymmetric unit, with a Matthews coefficient (VM) of 2.69,3,Da,1; the solvent content was estimated to be 54.3%. X-ray fluorescence spectroscopy and MAD diffraction data indicated the presence of manganese in the molecule and the absence of iron. [source]


Spectroelectrochemical and Computational Studies on the Mechanism of Hypoxia Selectivity of Copper Radiopharmaceuticals

CHEMISTRY - A EUROPEAN JOURNAL, Issue 19 2008
Jason
Abstract Detailed chemical, spectroelectrochemical and computational studies have been used to investigate the mechanism of hypoxia selectivity of a range of copper radiopharmaceuticals. A revised mechanism involving a delicate balance between cellular uptake, intracellular reduction, reoxidation, protonation and ligand dissociation is proposed. This mechanism accounts for observed differences in the reported cellular uptake and washout of related copper bis(thiosemicarbazonato) complexes. Three copper and zinc complexes have been characterised by X-ray crystallography and the redox chemistry of a series of copper complexes has been investigated by using electronic absorption and EPR spectroelectrochemistry. Time-dependent density functional theory (TD-DFT) calculations have also been used to probe the electronic structures of intermediate species and assign the electronic absorption spectra. DFT calculations also show that one-electron oxidation is ligand-based, leading to the formation of cationic triplet species. In the absence of protons, metal-centred one-electron reduction gives the reduced anionic copper(I) species, [CuIATSM],, and for the first time it is shown that molecular oxygen can reoxidise this anion to give the neutral, lipophilic parent complexes, which can wash out of cells. The electrochemistry is pH dependent and in the presence of stronger acids both chemical and electrochemical reduction leads to quantitative and rapid dissociation of copper(I) ions from the mono- or diprotonated complexes, [CuIATSMH] and [CuIATSMH2]+. In addition, a range of protonated intermediate species have been identified at lower acid concentrations. The one-electron reduction potential, rate of reoxidation of the copper(I) anionic species and ease of protonation are dependent on the structure of the ligand, which also governs their observed behaviour in vivo. [source]


Can Electrophilicity Act as a Measure of the Redox Potential of First-Row Transition Metal Ions?

CHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2007
Jan Moens
Abstract Previous contributions concerning the computational approach to redox chemistry have made use of thermodynamic cycles and Car,Parrinello molecular dynamics simulations to obtain accurate redox potential values, whereas this article adopts a conceptual density functional theory (DFT) approach. Conceptual DFT descriptors have found widespread use in the study of thermodynamic and kinetic aspects of a variety of organic and inorganic reactions. However, redox reactions have not received much attention until now. In this contribution, we prove the usefulness of global and local electrophilicity descriptors for the prediction of the redox characteristics of first row transition metal ions (from Sc3+|Sc2+ to Cu3+|Cu2+) and introduce a scaled definition of the electrophilicity based on the number of electrons an electrophile ideally accepts. This scaled electrophilicity concept acts as a good quantitative estimate of the redox potential. We also identify the first solvation sphere together with the metal ion as the primary active region during the electron uptake process, whereas the second solvation sphere functions as a non-reactive continuum region. [source]


A Theoretical Study of Surface Reduction Mechanisms of CeO2(111) and (110) by H2

CHEMPHYSCHEM, Issue 6 2007
Hsin-Tsung Chen Dr.
Abstract Reaction mechanisms for the interactions between CeO2(111) and (110) surfaces are investigated using periodic density functional theory (DFT) calculations. Both standard DFT and DFT+U calculations to examine the effect of the localization of Ce 4f states on the redox chemistry of H2,CeO2 interactions are described. For mechanistic studies, molecular and dissociative local minima are initially located by placing an H2 molecule at various active sites of the CeO2 surfaces. The binding energies of physisorbed species optimized using the DFT and DFT+U methods are very weak. The dissociative adsorption reactions producing hydroxylated surfaces are all exothermic; exothermicities at the DFT level range from 4.1 kcal,mol,1 for the (111) to 26.5 kcal,mol,1 for the (110) surface, while those at the DFT+U level are between 65.0 kcal,mol,1 for the (111) and 81.8 kcal,mol,1 for the (110) surface. Predicted vibrational frequencies of adsorbed OH and H2O species on the surfaces are in line with available experimental and theoretical results. Potential energy profiles are constructed by connecting molecularly adsorbed and dissociatively adsorbed intermediates on each CeO2 surface with tight transition states using the nudged elastic band (NEB) method. It is found that the U correction method plays a significant role in energetics, especially for the intermediates of the exit channels and products that are partially reduced. The surface reduction reaction on CeO2(110) is energetically much more favorable. Accordingly, oxygen vacancies are more easily formed on the (110) surface than on the (111) surface. [source]