Showing papers on "Redox published in 2014"

Copper Active Sites in Biology

Abstract: Based on its generally accessible I/II redox couple and bioavailability, copper plays a wide variety of roles in nature that mostly involve electron transfer (ET), O2 binding, activation and reduction, NO2− and N2O reduction and substrate activation. Copper sites that perform ET are the mononuclear blue Cu site that has a highly covalent CuII-S(Cys) bond and the binuclear CuA site that has a Cu2S(Cys)2 core with a Cu-Cu bond that keeps the site delocalized (Cu(1.5)2) in its oxidized state. In contrast to inorganic Cu complexes, these metalloprotein sites transfer electrons rapidly often over long distances, as has been previously reviewed.1–4 Blue Cu and CuA sites will only be considered here in their relation to intramolecular ET in multi-center enzymes. The focus of this review is on the Cu enzymes (Figure 1). Many are involved in O2 activation and reduction, which has mostly been thought to involve at least two electrons to overcome spin forbiddenness and the low potential of the one electron reduction to superoxide (Figure 2).5,6 Since the Cu(III) redox state has not been observed in biology, this requires either more than one Cu center or one copper and an additional redox active organic cofactor. The latter is formed in a biogenesis reaction of a residue (Tyr) that is also Cu catalyzed in the first turnover of the protein. Recently, however, there have been a number of enzymes suggested to utilize one Cu to activate O2 by 1e− reduction to form a Cu(II)-O2•− intermediate (an innersphere redox process) and it is important to understand the active site requirements to drive this reaction. The oxidases that catalyze the 4e−reduction of O2 to H2O are unique in that they effectively perform this reaction in one step indicating that the free energy barrier for the second two-electron reduction of the peroxide product of the first two-electron step is very low. In nature this requires either a trinuclear Cu cluster (in the multicopper oxidases) or a Cu/Tyr/Heme Fe cluster (in the cytochrome oxidases). The former accomplishes this with almost no overpotential maximizing its ability to oxidize substrates and its utility in biofuel cells, while the latter class of enzymes uses the excess energy to pump protons for ATP synthesis. In bacterial denitrification, a mononuclear Cu center catalyzes the 1e- reduction of nitrite to NO while a unique µ4S2−Cu4 cluster catalyzes the reduction of N2O to N2 and H2O, a 2e− process yet requiring 4Cu’s. Finally there are now several classes of enzymes that utilize an oxidized Cu(II) center to activate a covalently bound substrate to react with O2. Figure 1 Copper active sites in biology. Figure 2 Latimer Diagram for Oxygen Reduction at pH = 7.0 Adapted from References 5 and 6. This review presents in depth discussions of all these classes of Cu enzymes and the correlations within and among these classes. For each class we review our present understanding of the enzymology, kinetics, geometric structures, electronic structures and the reaction mechanisms these have elucidated. While the emphasis here is on the enzymology, model studies have significantly contributed to our understanding of O2 activation by a number of Cu enzymes and are included in appropriate subsections of this review. In general we will consider how the covalency of a Cu(II)–substrate bond can activate the substrate for its spin forbidden reaction with O2, how in binuclear Cu enzymes the exchange coupling between Cu’s overcomes the spin forbiddenness of O2 binding and controls electron transfer to O2 to direct catalysis either to perform two e− electrophilic aromatic substitution or 1e− H-atom abstraction, the type of oxygen intermediate that is required for H-atom abstraction from the strong C-H bond of methane (104 kcal/mol) and how the trinuclear Cu cluster and the Cu/Tyr/Heme Fe cluster achieve their very low barriers for the reductive cleavage of the O-O bond. Much of the insight available into these mechanisms in Cu biochemistry has come from the application of a wide range of spectroscopies and the correlation of spectroscopic results to electronic structure calculations. Thus we start with a tutorial on the different spectroscopic methods utilized to study mononuclear and multinuclear Cu enzymes and their correlations to different levels of electronic structure calculations.

The electron is a catalyst

Abstract: This Review draws an analogy between acid–base catalysis and redox catalysis. The 'electron is a catalyst' paradigm unifies mechanistically an assortment of synthetic transformations that otherwise have little or no apparent relationship. Various radical cascades catalysed by the electron are discussed.

Influence of the Donor Size in D−π–A Organic Dyes for Dye-Sensitized Solar Cells

Abstract: We report two new molecularly engineered push–pull dyes, i.e., YA421 and YA422, based on substituted quinoxaline as a π-conjugating linker and bulky-indoline moiety as donor and compared with reported IQ4 dye. Benefitting from increased steric hindrance with the introduction of bis(2,4-dihexyloxy)benzene substitution on the quinoxaline, the electron recombination between redox electrolyte and the TiO2 surface is reduced, especially in redox electrolyte employing Co(II/III) complexes as redox shuttles. It was found that the open circuit photovoltages of IQ4, YA421, and YA422 devices with cobalt-based electrolyte are higher than those with iodide/triiodide electrolyte by 34, 62, and 135 mV, respectively. Moreover, the cells employing graphene nanoplatelets on top of gold spattered film as a counter electrode (CE) show lower charge-transfer resistance compared to platinum as a CE. Consequently, YA422 devices deliver the best power conversion efficiency due to higher fill factor, reaching 10.65% at AM 1.5 sim...

Melanins: Skin Pigments and Much More—Types, Structural Models, Biological Functions, and Formation Routes

Abstract: This review presents a general view of all types of melanin in all types of organisms. Melanin is frequently considered just an animal cutaneous pigment and is treated separately from similar fungal or bacterial pigments. Similarities concerning the phenol precursors and common patterns in the formation routes are discussed. All melanins are formed in a first enzymatically-controlled phase, generally a phenolase, and a second phase characterized by an uncontrolled polymerization of the oxidized intermediates. In that second phase, quinones derived from phenol oxidation play a crucial role. Concerning functions, all melanins show a common feature, a protective role, but they are not merely photoprotective pigments against UV sunlight. In pathogenic microorganisms, melanization becomes a virulence factor since melanin protects microbial cells from defense mechanisms in the infected host. In turn, some melanins are formed in tissues where sunlight radiation is not a potential threat. Then, their redox, metal chelating, or free radical scavenging properties are more important than light absorption capacity. These pigments sometimes behave as a double-edged sword, and inhibition of melanogenesis is desirable in different cells. Melanin biochemistry is an active field of research from dermatological, biomedical, cosmetical, and microbiological points of view, as well as fruit technology.

Activation of Molecular Oxygen and the Nature of the Active Oxygen Species for CO Oxidation on Oxide Supported Au Catalysts

Abstract: Although highly dispersed Au catalysts with Au nanoparticles (NPs) of a few nanometers in diameter are well-known for their high catalytic activity for several oxidation and reduction reactions already at rather low temperatures for almost 30 years, central aspects of the reaction mechanism are still unresolved. While most studies focused on the active site, the active Au species, and the effect of the support material, the most crucial step during oxidation reactions, the activation of molecular oxygen and the nature of the resulting active oxygen species (Oact), received more attention just recently.This is topic of this Account, which focuses on the formation, location, and nature of the Oact species present on metal oxide supported Au catalysts under typical reaction conditions, at room temperature and above. It is mainly based on quantitative temporal analysis of products (TAP) reactor measurements, which different from most spectroscopic techniques are able to detect and quantify these species even ...

Novel Mn–Ce–Ti Mixed-Oxide Catalyst for the Selective Catalytic Reduction of NOx with NH3

Abstract: Mn-Ce-Ti mixed-oxide catalyst prepared by the hydrothermal method was investigated for the selective catalytic reduction (SCR) of NOx with NH3 in the presence of oxygen. It was found that the environmentally benign Mn-Ce-Ti catalyst exhibited excellent NH3-SCR activity and strong resistance against H2O and SO2 with a broad operation temperature window, which is very competitive for the practical application in controlling the NOx emission from diesel engines. On the basis of the catalyst characterization, the dual redox cycles (Mn4+ + Ce3+ Mn3+ + Ce4+, Mn4+ + Ti3+ Mn3+ + Ti4+) and the amorphous structure play key roles for the high catalytic deNO(x) performance. Diffuse reflectance infrared Fourier transform spectroscopy studies showed that the synergetic effect between Mn and Ce contributes to the formation of reactive intermediate species, thus promoting the NH3-SCR to proceed.

Photochemical Reduction of CO2 by Graphitic Carbon Nitride Polymers

Abstract: The combination of cobalt redox catalysis and carbon nitride photocatalysis to construct a cascade photoreaction system has been developed for the deoxygenative reduction of CO2 to CO with visible light. The graphitic carbon nitride has been demonstrated to function both as a capture/activation substrate of CO2 and a photocatalyst, whereas the introduced cobalt species act as reductive and oxidative promoters to accelerate charge-carrier separation and transfer kinetics. This hybrid photosystem contains inexpensive substances that synergetically catalyze CO2-to-CO conversion at mild conditions, with a high stability of catalysts. The optimization in the surface and texture structures as well as reaction conditions has been demonstrated. The results represent an important step toward artificial photosynthesis by using cost-acceptable materials.

Trends in electrochemical CO2 reduction activity for open and close-packed metal surfaces

Abstract: We present a theoretical analysis of trends in overpotentials for electrocatalytic CO2 reduction based on density functional theory calculations. The analysis is based on understanding variations in the free energy of intermediates and mapping out the potential at which different elementary steps are exergonic as a measure of the catalytic activity. We study different surface structures and introduce a simple model for including the effect of adsorbate–adsorbate interactions. We find that high coverages of CO under typical reaction conditions for the more reactive transition metals affect the catalytic activity towards the CO2 reduction reaction, but the ordering of metal activities is not changed. For the hydrogen evolution reaction, a high CO coverage shifts the maximum activity towards more reactive metals than Pt.

Unravelling the Structure of Electrocatalytically Active Fe–N Complexes in Carbon for the Oxygen Reduction Reaction

Abstract: Non-precious Fe/N co-modified carbon electrocatalysts have attracted great attention due to their high activity and stability in oxygen reduction reaction (ORR). Compared to iron-free N-doped carbon electrocatalysts, Fe/N-modified electrocatalysts show four-electron selectivity with better activity in acid electrolytes. This is believed relevant to the unique Fe-N complexes, however, the Fe-N structure remains unknown. We used o,m,p-phenylenediamine as nitrogen precursors to tailor the Fe-N structures in heterogeneous electrocatalysts which contain FeS and Fe3C phases. The electrocatalysts have been operated for 5000 cycles with a small 39 mV shift in half-wave potential. By combining advanced electron microscopy and Mossbauer spectroscopy, we have identified the electrocatalytically active Fe-N-6 complexes (FeN6, [FeIII(porphyrin)(pyridine)(2)]). We expect the understanding of the FeN6 structure will pave the way towards new advanced Fe-N based electrocatalysts.

Gold Atoms Stabilized on Various Supports Catalyze the Water–Gas Shift Reaction

Abstract: For important chemical reactions that are catalyzed by single-site metal centers, such as the water–gas shift (WGS) reaction that converts carbon monoxide and water to hydrogen and carbon dioxide, atomically dispersed supported metal catalysts offer maximum atom efficiency. Researchers have found that for platinum metal supported on ceria and doped ceria in the automobile exhaust catalyst, atomic Pt–Ox–Ce species are the active WGS reaction sites. More recently, preparations of gold at the nanoscale have shown that this relatively “new material” is an active and often more selective catalyst than platinum for a variety of reactions, including the WGS reaction. The activity of gold is typically attributed to a size effect, while the interface of gold with the support has also been reported as important for oxidation reactions, but exactly how this comes about has not been probed satisfactorily. Typical supported metal catalysts prepared by traditional techniques have a heterogeneous population of particles...

Nanoparticle conversion chemistry: Kirkendall effect, galvanic exchange, and anion exchange

Abstract: Conversion chemistry is a rapidly maturing field, where chemical conversion of template nanoparticles (NPs) into new compositions is often accompanied by morphological changes, such as void formation. The principles and examples of three major classes of conversion chemical reactions are reviewed: the Kirkendall effect for metal NPs, galvanic exchange, and anion exchange, each of which can result in void formation in NPs. These reactions can be used to obtain complex structures that may not be attainable by other methods. During each kind of conversion chemical reaction, NPs undergo distinct chemical and morphological changes, and insights into the mechanisms of these reactions will allow for improved fine control and prediction of the structures of intermediates and products. Conversion of metal NPs into oxides, phosphides, sulphides, and selenides often occurs through the Kirkendall effect, where outward diffusion of metal atoms from the core is faster than inward diffusion of reactive species, resulting in void formation. In galvanic exchange reactions, metal NPs react with noble metal salts, where a redox reaction favours reduction and deposition of the noble metal (alloying) and oxidation and dissolution of the template metal (dealloying). In anion exchange reactions, addition of certain kinds of anions to solutions containing metal compound NPs drives anion exchange, which often results in significant morphological changes due to the large size of anions compared to cations. Conversion chemistry thus allows for the formation of NPs with complex compositions and structures, for which numerous applications are anticipated arising from their novel catalytic, electronic, optical, magnetic, and electrochemical properties.

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu‐SSZ‐13

Abstract: Operando X-ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu-exchanged SSZ-13. Catalysts prepared to contain only isolated, exchanged CuII ions evidence both CuII and CuI ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH3 together are necessary for CuII reduction to CuI. DFT calculations show that NO-assisted NH3 dissociation is both energetically favorable and accounts for the observed CuII reduction. The calculations predict in situ generation of Bronsted sites proximal to CuI upon reduction, which we quantify in separate titration experiments. Both NO and O2 are necessary for oxidation of CuI to CuII, which DFT suggests to occur by a NO2 intermediate. Reaction of Cu-bound NO2 with proximal NH4+ completes the catalytic cycle. N2 is produced in both reduction and oxidation half-cycles.

Oxalate route for promoting activity of manganese oxide catalysts in total VOCs’ oxidation: effect of calcination temperature and preparation method

Abstract: A novel template-free oxalate route was applied to synthesize mesoporous manganese oxides with high surface area (355 m2 g−1) and well-defined mesopores which can be obtained in large quantities. The physicochemical properties of the materials were characterized by means of TG, XRD, SEM, TEM, H2-TPR and XPS techniques. All catalysts were tested on catalytic deep oxidation of benzene, and the effects of calcination temperature on the features of catalyst structure and catalytic activity were investigated. Manganese oxides prepared by oxalate route exhibited better catalytic activities for complete oxidation of benzene, toluene and o-xylene as compared with related manganese oxides prepared by other different methods (NaOH route, NH4HCO3 route and nanocasting strategy), and especially the temperature for benzene conversion of 90% on the oxalate-derived manganese oxide catalysts was 209 °C, which is 132 °C lower than required for the catalyst prepared by NaOH route. The catalytic performance of manganese oxide is correlated with surface area, pore size, low-temperature reducibility and distribution of surface species. The mole ratio of Mn4+/Mn2+ on the samples which performed with better catalytic activity was close to 1.0. This is good for the redox process of Mn4+ ↔ Mn3+ ↔ Mn2+ which is the key factor in determining the activity on MnOx, further indicating that the oxalate route is good for keeping the distribution of manganese oxidation states at an appropriate degree. A possible process of VOCs’ complete oxidation on manganese oxide catalysts is discussed. In addition, the best catalyst was highly stable with prolonged time on stream and was resistant to water vapor.

Redox regulation of mitochondrial function with emphasis on cysteine oxidation reactions

Abstract: Mitochondria have a myriad of essential functions including metabolism and apoptosis These chief functions are reliant on electron transfer reactions and the production of ATP and reactive oxygen species (ROS) The production of ATP and ROS are intimately linked to the electron transport chain (ETC) Electrons from nutrients are passed through the ETC via a series of acceptor and donor molecules to the terminal electron acceptor molecular oxygen (O2) which ultimately drives the synthesis of ATP Electron transfer through the respiratory chain and nutrient oxidation also produces ROS At high enough concentrations ROS can activate mitochondrial apoptotic machinery which ultimately leads to cell death However, if maintained at low enough concentrations ROS can serve as important signaling molecules Various regulatory mechanisms converge upon mitochondria to modulate ATP synthesis and ROS production Given that mitochondrial function depends on redox reactions, it is important to consider how redox signals modulate mitochondrial processes Here, we provide the first comprehensive review on how redox signals mediated through cysteine oxidation, namely S-oxidation (sulfenylation, sulfinylation), S-glutathionylation, and S-nitrosylation, regulate key mitochondrial functions including nutrient oxidation, oxidative phosphorylation, ROS production, mitochondrial permeability transition (MPT), apoptosis, and mitochondrial fission and fusion We also consider the chemistry behind these reactions and how they are modulated in mitochondria In addition, we also discuss emerging knowledge on disorders and disease states that are associated with deregulated redox signaling in mitochondria and how mitochondria-targeted medicines can be utilized to restore mitochondrial redox signaling

Monitoring the Solid-State Electrochemistry of Cu(2,7-AQDC) (AQDC = Anthraquinone Dicarboxylate) in a Lithium Battery: Coexistence of Metal and Ligand Redox Activities in a Metal–Organic Framework

Abstract: By adopting a facile synthetic strategy, we obtained a microporous redox-active metal-organic framework (MOF), namely, Cu(2,7-AQDC) (2,7-H2AQDC = 2,7-anthraquinonedicarboxylic acid) (1), and utilized it as a cathode active material in lithium batteries. With a voltage window of 4.0-1.7 V, both metal clusters and anthraquinone groups in the ligands exhibited reversible redox activity. The valence change of copper cations was clearly evidenced by in situ XANES analysis. By controlling the voltage window of operation, extremely high recyclability of batteries was achieved, suggesting the framework was robust. This MOF is the first example of a porous material showing independent redox activity on both metal cluster nodes and ligand sites.

Selective aerobic oxidation mediated by TiO(2) photocatalysis.

Abstract: TiO2 is one of the most studied metal oxide photocatalysts and has unparal-leled efficiency and stability. This cheap, abundant, and non-toxic material has the potential to address future environmental and energy concerns. Understanding about the photoinduced interfacial redox events on TiO2 could have profound effect on the degradation of organic pollutants, splitting of H2O into H2 and O2, and selective redox organic transformations. Scientists traditionally accept that for a semiconductor photocatalyst such as TiO2 under the illumination of light with energy larger than its band gap, two photocarriers will be created to carry out their independent reduction and oxidation processes. However, our recent discoveries indicate that it is the concerted rather than independent effect of both photocarriers of valence band hole (hvb(+)) and conduction band electron (ecb(-)) that dictate the product formation during interfacial oxidation event mediated by TiO2 photocatalysis. In this Account, we describe our recent findings on the selective oxidation of organic substrates with O2 mediated by TiO2 photocatalysis. The transfer of O-atoms from O2 to the corresponding products dominates the selective oxidation of alcohols, amines, and alkanes mediated by TiO2 photocatalysis. We ascribe this to the concerted effect of both hvb(+) and ecb(-) of TiO2 in contribution to the oxidation products. These findings imply that O2 plays a unique role in its transfer into the products rather than independent role of ecb(-) scavenger. More importantly, ecb(-) plays a crucial role to ensure the high selectivity for the oxygenation of organic substrates. We can also use the half reactions such as those of the conduction band electron of TiO2 for efficient oxidation reactions with O2. To this end, efficient selective oxidation of organic substrates such as alcohols, amines, and aromatic alkanes with O2 mediated by TiO2 photocatalysis under visible light irradiation has been achieved. In summary, the concerted effect of hvb(+) and ecb(-) to implement one oxidation event could pave the way for selective oxofunctionalization of organic substrates with O2 by metal oxide photocatalysis. Furthermore, it could also deepen our understanding on the role of O2 and the elusive nature of oxygen species at the interface of TiO2, which, in turn, could shed new light on avant-garde photocatalytic selective redox processes in addressing the energy and environmental challenges of the future.

Long-Range Electron Tunneling

Abstract: Electrons have so little mass that in less than a second they can tunnel through potential energy barriers that are several electron-volts high and several nanometers wide. Electron tunneling is a critical functional element in a broad spectrum of applications, ranging from semiconductor diodes to the photosynthetic and respiratory charge transport chains. Prior to the 1970s, chemists generally believed that reactants had to collide in order to effect a transformation. Experimental demonstrations that electrons can transfer between reactants separated by several nanometers led to a revision of the chemical reaction paradigm. Experimental investigations of electron exchange between redox partners separated by molecular bridges have elucidated many fundamental properties of these reactions, particularly the variation of rate constants with distance. Theoretical work has provided critical insights into the superexchange mechanism of electronic coupling between distant redox centers. Kinetics measurements have shown that electrons can tunnel about 2.5 nm through proteins on biologically relevant time scales. Longer-distance biological charge flow requires multiple electron tunneling steps through chains of redox cofactors. The range of phenomena that depends on long-range electron tunneling continues to expand, providing new challenges for both theory and experiment.

On the Direct Electron Transfer, Sensing, and Enzyme Activity in the Glucose Oxidase/Carbon Nanotubes System

Abstract: The signal transduction and enzyme activity were investigated in biosensors based on the glucose oxidase (GOx) and carbon nanotubes (CNT) embedded in a bioadhesive film of chitosan (CHIT) The voltammetric studies showed that, regardless of CHIT matrix, the GOx adsorbed on CNT yielding a pair of surface-confined current peaks at −048 V The anodic peak did not increase in the presence of glucose in an O2-free solution indicating the lack of direct electron transfer (DET) between the enzymatically active GOx and CNT The voltammetric peaks were due to the redox of enzyme cofactor flavin adenine dinucleotide (FAD), which was not the part of active enzyme The presented data suggest that DET may not be happening for any type of GOx/CNT-based sensor The biosensor was sensitive to glucose in air-equilibrated solutions indicating the O2-mediated enzymatic oxidation of glucose The signal transduction relied on the net drop in a biosensor current that was caused by a decrease in a 4-e– O2 reduction current and

Corn protein-derived nitrogen-doped carbon materials with oxygen-rich functional groups: a highly efficient electrocatalyst for all-vanadium redox flow batteries

Abstract: Recent studies on all-vanadium redox flow batteries (VRFBs) have focused on carbon-based materials for cost-effective electrocatalysts to commercialize them in grid-scale energy storage markets. We report an environmentally friendly and safe method to produce carbon-based catalysts by corn protein self-assembly. This new method allows carbon black (CB) nanoparticles to be coated with nitrogen-doped graphitic layers with oxygen-rich functionalities (N-CB). We observed increased catalytic activity of this catalyst toward both V2+/V3+ and VO2+/VO2+ ions, showing a 24% increased mass transfer process and ca. 50 mV higher reduction onset potential compared to CB catalyst. It is believed that the abundant oxygen active sites and nitrogen defects in the N-CB catalyst are beneficial to the vanadium redox reaction by improving the electron transfer rate and giving faster vanadium ion transfer kinetics.

Probing the Lithium−Sulfur Redox Reactions: A Rotating-Ring Disk Electrode Study

Abstract: Detailed mechanistic understanding of sulfur redox reactions is critical for developing efficient and stable lithium–sulfur batteries. Here, we employ the rotating-ring disk electrode technique to probe the reaction kinetics and reaction mechanism of lithium–sulfur redox reactions in dimethyl sulfoxide and 1,3-dioxolane:1,2-dimethoxyethane. We quantitatively determine the number of electrons involved in the reduction reactions and the specific activity of sulfur reduction reactions. We show that the electrochemical steps of sulfur reduction exhibit fast reaction kinetics and only account for approximately one-quarter of the total capacity (i.e., ≈4 e–/S8) within the short reaction time in RRDE experiments (seconds). The complete conversion of sulfur to Li2S can only be accomplished via chemical (i.e., potential-independent) polysulfide recombination/dissociation reactions that generate electrochemically reducible polysulfides with long reaction time (hours) in a closed battery cell. The influence of the s...

Investigation of the structure, acidity, and catalytic performance of CuO/Ti0.95Ce0.05O2 catalyst for the selective catalytic reduction of NO by NH3 at low temperature

Abstract: Anatase TiO2, Ti0.95Ce0.05O2 solid solution, and CeO2 were synthesized by inverse co-precipitation method, and then used as supports to prepare CuO/TiO2, CuO/Ti0.95Ce0.05O2, and CuO/CeO2 catalysts through incipient-wetness impregnation method. The obtained samples were investigated in detail by means of N2-physisorption, XRD, LRS, H2-TPR, XPS, NH3-TPD, and in situ DRIFTS technologies. Furthermore, NH3-SCR of NO in the presence of excess oxygen was chosen as a model reaction to evaluate the catalytic performances of these samples. The obtained results indicate that the incorporation of Ce4+ into the lattice of anatase TiO2 leads to the formation of unstable distorted octahedral coordination structure of Cu2+ in CuO/Ti0.95Ce0.05O2 catalyst and the enhancement of the electron interaction between copper oxide species and Ti0.95Ce0.05O2 support through the redox cycles of Cu2+ + Ce3+ ↔ Cu+ + Ce4+ and Cu2+ + Ti3+ ↔ Cu+ + Ti4+, which are beneficial to the formation of more Lewis acid sites on the surface of CuO/Ti0.95Ce0.05O2 catalyst and the activation of reactant molecules to generate more NH4NO2 species, all of these may promote the enhancement of catalytic performance for NH3-SCR of NO in the presence of excess oxygen. Finally, a possible reaction mechanism (schematic diagram) is tentatively proposed to further understand this model reaction.

A redox hydrogel protects hydrogenase from high-potential deactivation and oxygen damage

Abstract: Hydrogenases are nature's efficient catalysts for both the generation of energy via oxidation of molecular hydrogen and the production of hydrogen via the reduction of protons. However, their O2 sensitivity and deactivation at high potential limit their applications in practical devices, such as fuel cells. Here, we show that the integration of an O2-sensitive hydrogenase into a specifically designed viologen-based redox polymer protects the enzyme from O2 damage and high-potential deactivation. Electron transfer between the polymer-bound viologen moieties controls the potential applied to the active site of the hydrogenase and thus insulates the enzyme from excessive oxidative stress. Under catalytic turnover, electrons provided from the hydrogen oxidation reaction induce viologen-catalysed O2 reduction at the polymer surface, thus providing self-activated protection from O2. The advantages of this tandem protection are demonstrated using a single-compartment biofuel cell based on an O2-sensitive hydrogenase and H2/O2 mixed feed under anode-limiting conditions.

Bioinspired copper catalyst effective for both reduction and evolution of oxygen

Abstract: In many green electrochemical energy devices, the conversion between oxygen and water suffers from high potential loss due to the difficulty in decreasing activation energy. Overcoming this issue requires full understanding of global reactions and development of strategies in efficient catalyst design. Here we report an active copper nanocomposite, inspired by natural coordination environments of catalytic sites in an enzyme, which catalyzes oxygen reduction/evolution at potentials closely approaching standard potential. Such performances are related to the imperfect coordination configuration of the copper(II) active site whose electron density is tuned by neighbouring copper(0) and nitrogen ligands incorporated in graphene. The electron transfer number of oxygen reduction is estimated by monitoring the redox of hydrogen peroxide, which is determined by the overpotential and electrolyte pH. An in situ fluorescence spectroelectrochemistry reveals that hydroxyl radical is the common intermediate for the electrochemical conversion between oxygen and water.

Structural Changes in Li2MnO3 Cathode Material for Li‐Ion Batteries

Abstract: Structural changes in Li2MnO3 cathode material for rechargeable Li-ion batteries are investigated during the first and 33rd cycles. It is found that both the participation of oxygen anions in redox processes and Li+-H+ exchange play an important role in the electrochemistry of Li2MnO3. During activation, oxygen removal from the material along with Li gives rise to the formation of a layered MnO2-type structure, while the presence of protons in the interslab region, as a result of electrolyte oxidation and Li+-H+ exchange, alters the stacking sequence of oxygen layers. Li re-insertion by exchanging already present protons reverts the stacking sequence of oxygen layers. The re-lithiated structure closely resembles the parent Li2MnO3, except that it contains less Li and O. Mn4+ ions remain electrochemically inactive at all times. Irreversible oxygen release occurs only during activation of the material in the first cycle. During subsequent cycles, electrochemical processes seem to involve unusual redox processes of oxygen anions of active material along with the repetitive, irreversible oxidation of electrolyte species. The deteriorating electrochemical performance of Li2MnO3 upon cycling is attributed to the structural degradation caused by repetitive shearing of oxygen layers.

Development of Double-Perovskite Compounds as Cathode Materials for Low-Temperature Solid Oxide Fuel Cells

Abstract: A class of double-perovskite compounds display fast oxygen ion diffusion and high catalytic activity toward oxygen reduction while maintaining excellent compatibility with the electrolyte. The astoundingly extended stability of NdBa1−xCaxCo2O5+δ (NBCaCO) under both air and CO2-containing atmosphere is reported along with excellent electrochemical performance by only Ca doping into the A site of NdBaCo2O5+δ (NBCO). The enhanced stability can be ascribed to both the increased electron affinity of mobile oxygen species with Ca, determined through density functional theory calculations and the increased redox stability from the coulometric titration.