Showing papers on "Oxide published in 2018"

Enhanced strength and ductility in a high-entropy alloy via ordered oxygen complexes

Abstract: Oxygen, one of the most abundant elements on Earth, often forms an undesired interstitial impurity or ceramic phase (such as an oxide particle) in metallic materials. Even when it adds strength, oxygen doping renders metals brittle1–3. Here we show that oxygen can take the form of ordered oxygen complexes, a state in between oxide particles and frequently occurring random interstitials. Unlike traditional interstitial strengthening4,5, such ordered interstitial complexes lead to unprecedented enhancement in both strength and ductility in compositionally complex solid solutions, the so-called high-entropy alloys (HEAs)6–10. The tensile strength is enhanced (by 48.5 ± 1.8 per cent) and ductility is substantially improved (by 95.2 ± 8.1 per cent) when doping a model TiZrHfNb HEA with 2.0 atomic per cent oxygen, thus breaking the long-standing strength–ductility trade-off11. The oxygen complexes are ordered nanoscale regions within the HEA characterized by (O, Zr, Ti)-rich atomic complexes whose formation is promoted by the existence of chemical short-range ordering among some of the substitutional matrix elements in the HEAs. Carbon has been reported to improve strength and ductility simultaneously in face-centred cubic HEAs12, by lowering the stacking fault energy and increasing the lattice friction stress. By contrast, the ordered interstitial complexes described here change the dislocation shear mode from planar slip to wavy slip, and promote double cross-slip and thus dislocation multiplication through the formation of Frank–Read sources (a mechanism explaining the generation of multiple dislocations) during deformation. This ordered interstitial complex-mediated strain-hardening mechanism should be particularly useful in Ti-, Zr- and Hf-containing alloys, in which interstitial elements are highly undesirable owing to their embrittlement effects, and in alloys where tuning the stacking fault energy and exploiting athermal transformations13 do not lead to property enhancement. These results provide insight into the role of interstitial solid solutions and associated ordering strengthening mechanisms in metallic materials. Ordered oxygen complexes in high-entropy alloys enhance both strength and ductility in these compositionally complex solid solutions.

Review of Hybrid Ion Capacitors: From Aqueous to Lithium to Sodium.

Abstract: In this critical Review we focus on the evolution of the hybrid ion capacitor (HIC) from its early embodiments to its modern form, focusing on the key outstanding scientific and technological questions that necessitate further in-depth study. It may be argued that HICs began as aqueous systems, based on a Faradaic oxide positive electrode (e.g., Co3O4, RuOx) and an activated carbon ion-adsorption negative electrode. In these early embodiments HICs were meant to compete directly with electrical double layer capacitors (EDLCs), rather than with the much higher energy secondary batteries. The HIC design then evolved to be based on a wide voltage (∼4.2 V) carbonate-based battery electrolyte, using an insertion titanium oxide compound anode (Li4Ti5O12, LixTi5O12) versus a Li ion adsorption porous carbon cathode. The modern Na and Li architectures contain a diverse range of nanostructured materials in both electrodes, including TiO2, Li7Ti5O12, Li4Ti5O12, Na6LiTi5O12, Na2Ti3O7, graphene, hard carbon, soft carbo...

Defect Effects on TiO2 Nanosheets: Stabilizing Single Atomic Site Au and Promoting Catalytic Properties.

Abstract: Isolated single atomic site catalysts have attracted great interest due to their remarkable catalytic properties Because of their high surface energy, single atoms are highly mobile and tend to form aggregate during synthetic and catalytic processes Therefore, it is a significant challenge to fabricate isolated single atomic site catalysts with good stability Herein, a gentle method to stabilize single atomic site metal by constructing defects on the surface of supports is presented As a proof of concept, single atomic site Au supported on defective TiO2 nanosheets is prepared and it is discovered that (1) the surface defects on TiO2 nanosheets can effectively stabilize Au single atomic sites through forming the Ti-Au-Ti structure; and (2) the Ti-Au-Ti structure can also promote the catalytic properties through reducing the energy barrier and relieving the competitive adsorption on isolated Au atomic sites It is believed that this work paves a way to design stable and active single atomic site catalysts on oxide supports

Efficient hydrogen peroxide generation using reduced graphene oxide-based oxygen reduction electrocatalysts

Abstract: Electrochemical oxygen reduction has garnered attention as an emerging alternative to the traditional anthraquinone oxidation process to enable the distributed production of hydrogen peroxide. Here, we demonstrate a selective and efficient non-precious electrocatalyst, prepared through an easily scalable mild thermal reduction of graphene oxide, to form hydrogen peroxide from oxygen. During oxygen reduction, certain variants of the mildly reduced graphene oxide electrocatalyst exhibit highly selective and stable peroxide formation activity at low overpotentials (<10 mV) under basic conditions, exceeding the performance of current state-of-the-art alkaline catalysts. Spectroscopic structural characterization and in situ Raman spectroelectrochemistry provide strong evidence that sp2-hybridized carbon near-ring ether defects along sheet edges are the most active sites for peroxide production, providing new insight into the electrocatalytic design of carbon-based materials for effective peroxide production. Electrochemical routes for the production of hydrogen peroxide would reduce the waste inherent in the current anthraquinone process, and also make distributed and on-site production more feasible. Here, inexpensive reduced graphene oxide is proven to be a stable and selective catalyst for oxygen reduction at remarkably low overpotentials.

High entropy oxides for reversible energy storage

Abstract: In recent years, the concept of entropy stabilization of crystal structures in oxide systems has led to an increased research activity in the field of “high entropy oxides”. These compounds comprise the incorporation of multiple metal cations into single-phase crystal structures and interactions among the various metal cations leading to interesting novel and unexpected properties. Here, we report on the reversible lithium storage properties of the high entropy oxides, the underlying mechanisms governing these properties, and the influence of entropy stabilization on the electrochemical behavior. It is found that the stabilization effect of entropy brings significant benefits for the storage capacity retention of high entropy oxides and greatly improves the cycling stability. Additionally, it is observed that the electrochemical behavior of the high entropy oxides depends on each of the metal cations present, thus providing the opportunity to tailor the electrochemical properties by simply changing the elemental composition.

A review on chemiresistive room temperature gas sensors based on metal oxide nanostructures, graphene and 2D transition metal dichalcogenides

Abstract: Room-temperature (RT) gas sensing is desirable for battery-powered or self-powered instrumentation that can monitor emissions associated with pollution and industrial processes. This review (with 171 references) discusses recent advances in three types of porous nanostructures that have shown remarkable potential for RT gas sensing. The first group comprises hierarchical oxide nanostructures (mainly oxides of Sn, Ni, Zn, W, In, La, Fe, Co). The second group comprises graphene and its derivatives (graphene, graphene oxides, reduced graphene oxides, and their composites with metal oxides and noble metals). The third group comprises 2D transition metal dichalcogenides (mainly sulfides of Mo, W, Sn, Ni, also in combination with metal oxides). They all have been found to enable RT sensing of gases such as NOx, NH3, H2, SO2, CO, and of vapors such as of acetone, formaldehyde or methanol. Attractive features also include high selectivity and sensitivity, long-term stability and affordable costs. Strengths and limitations of these materials are highlighted, and prospects with respect to the development of new materials to overcome existing limitations are discussed.

Holey Reduced Graphene Oxide Coupled with an Mo2N–Mo2C Heterojunction for Efficient Hydrogen Evolution

Abstract: An in situ catalytic etching strategy is developed to fabricate holey reduced graphene oxide along with simultaneous coupling with a small-sized Mo2 N-Mo2 C heterojunction (Mo2 N-Mo2 C/HGr). The method includes the first immobilization of H3 PMo12 O40 (PMo12 ) clusters on graphite oxide (GO), followed by calcination in air and NH3 to form Mo2 N-Mo2 C/HGr. PMo12 not only acts as the Mo heterojunction source, but also provides the Mo species that can in situ catalyze the decomposition of adjacent reduced GO to form HGr, while the released gas (CO) and introduced NH3 simultaneously react with the Mo species to form an Mo2 N-Mo2 C heterojunction on HGr. The hybrid exhibits superior activity towards the hydrogen evolution reaction with low onset potentials of 11 mV (0.5 m H2 SO4 ) and 18 mV (1 m KOH) as well as remarkable stability. The activity in alkaline media is also superior to Pt/C at large current densities (>88 mA cm-2 ). The good activity of Mo2 N-Mo2 C/HGr is ascribed to its small size, the heterojunction of Mo2 N-Mo2 C, and the good charge/mass-transfer ability of HGr, as supported by a series of experiments and theoretical calculations.

Green synthesis of graphene oxide by seconds timescale water electrolytic oxidation

Abstract: Graphene oxide is highly desired for printing electronics, catalysis, energy storage, separation membranes, biomedicine, and composites. However, the present synthesis methods depend on the reactions of graphite with mixed strong oxidants, which suffer from explosion risk, serious environmental pollution, and long-reaction time up to hundreds of hours. Here, we report a scalable, safe and green method to synthesize graphene oxide with a high yield based on water electrolytic oxidation of graphite. The graphite lattice is fully oxidized within a few seconds in our electrochemical oxidation reaction, and the graphene oxide obtained is similar to those achieved by the present methods. We also discuss the synthesis mechanism and demonstrate continuous and controlled synthesis of graphene oxide and its use for transparent conductive films, strong papers, and ultra-light elastic aerogels.

Metal–Organic Framework Hybrid-Assisted Formation of Co3O4/Co-Fe Oxide Double-Shelled Nanoboxes for Enhanced Oxygen Evolution

Abstract: Rational design of complex metal-organic framework (MOF) hybrid precursors offers a great opportunity to construct various functional nanostructures. Here, a novel MOF-hybrid-assisted strategy to synthesize Co3 O4 /Co-Fe oxide double-shelled nanoboxes is reported. In the first step, zeolitic imidazolate framework-67 (ZIF-67, a Co-based MOF)/Co-Fe Prussian blue analogue (PBA) yolk-shell nanocubes are formed via a facile anion-exchange reaction between ZIF-67 nanocube precursors and [Fe(CN)6 ]3- ions at room temperature. Subsequently, an annealing treatment is applied to prepare Co3 O4 /Co-Fe oxide double-shelled nanoboxes. Owing to the structural and compositional benefits, the as-derived Co3 O4 /Co-Fe oxide double-shelled nanoboxes exhibit enhanced electrocatalytic performance for oxygen evolution reaction in alkaline solution.

Highly stable graphene-oxide-based membranes with superior permeability

Abstract: Increasing fresh water demand for drinking and agriculture is one of the grand challenges of our age. Graphene oxide (GO) membranes have shown a great potential for desalination and water purification. However, it is challenging to further improve the water permeability without sacrificing the separation efficiency, and the GO membranes are easily delaminated in aqueous solutions within few hours. Here, we report a class of reduced GO membranes with enlarged interlayer distance fabricated by using theanine amino acid and tannic acid as reducing agent and cross-linker. Such membranes show water permeance over 10,000 L m-2 h-1 bar-1, which is 10-1000 times higher than those of previously reported GO-based membranes and commercial membranes, and good separation efficiency, e.g., rhodamine B and methylene blue rejection of ~100%. Moreover, they show no damage or delamination in water, acid, and basic solutions even after months.

Aggregation-Resistant 3D MXene-Based Architecture as Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

Abstract: The MXene combining high conductivity, hydrophilic surface, and wide chemical variety has been recognized as a rapidly rising star on the horizon of two-dimensional (2D) material science. However, strong tendency to intersheet aggregate via van der Waals force represents a major problem limiting the functionalities, processability, and performance of MXene-based material/devices. We report a capillary-forced assembling strategy for processing MXene to hierarchical 3D architecture with geometry-based high resistance to aggregation. Aggregate-resistant properties of 3D MXene not only double the surface area without loss of the intrinsic properties of MXene but also render the characteristics such as kinetics-favorable framework, high robustness, and excellent processability in both solution and solid state. Synergistically coupling the 3D MXene with electrochemically active phases such as metal oxide/phosphides, noble metals, or sulfur yields the hybrid systems with greatly boosted active surface area, charge-transfer kinetics, and mass diffusion rate. Specifically, the CoP-3D MXene hybrids exhibit high electrocatalytic activity toward oxygen and hydrogen evolution in alkaline electrolyte. As a bifunctional electrocatalyst, they exhibit superior cell voltage and durability to combined RuO2/Pt catalysts for overall water splitting in basic solution, highlighting the great promise of aggregation-resistant 3D MXene in the development of high-performance electrocatalysts.

Antimicrobial Activity of Metal and Metal‐Oxide Based Nanoparticles

Abstract: With an increase in antibiotic resistance, a growing interest in developing new antimicrobial agents has gained popularity. Metal‐ and metal‐oxide‐based nanoparticles, surface‐to‐volume is able to distinguish bacterial cells from mammalian cells and can provide long‐term antibacterial and biofilm prevention. These nanoparticles elicit bactericidal properties through the generation of reactive oxygen species (ROS) that are able to target physical structures, metabolic pathways, and DNA synthesis of prokaryotic cells leading to cell death. In this progress report, a critical analysis of current literature on antimicrobial effect of metal and metal‐oxide nanoparticles are examined. Specifically, the antimicrobial mechanisms of metal ions and metal nanomaterials are discussed. Antimicrobial efficiency of nanomaterials is correlated with the structural and physical properties, such as size, shape, and/or zeta potential. A critical analysis of the current state of metal and metal‐oxide nanomaterial research advances our understanding to overcome antibiotic resistance and provide alternatives to combat bacterial infections. Finally, emerging approaches to identify and minimize metallic poisoning, specifically for biomedical applications, are examined.

A Stable Bifunctional Catalyst for Rechargeable Zinc–Air Batteries: Iron–Cobalt Nanoparticles Embedded in a Nitrogen‐Doped 3D Carbon Matrix

Abstract: Low-cost, efficient bifunctional electrocatalysts are needed to mediate the oxygen reduction and oxygen evolution reactions (ORR/OER) in Zn-air batteries. Such catalysts should offer binary active sites and an ability to transfer oxygen-based species and electrons. A 3D catalyst, composed of nanoparticles of CoFe alloy embedded in N-doped carbon nanotubes tangled with reduced graphene oxide, was developed, which presents appreciable ORR/OER activity when applied in a Zn-air battery. A high open-circuit voltage of 1.43 V, a stable discharge voltage of 1.22 V, a high energy efficiency of 60.1 %, and excellent stability after 1 600 cycles at 10 mA cm-2 are demonstrated. An all-solid-state battery had an outstanding lifetime and high cell efficiency even upon bending. In situ X-ray absorption spectroscopy revealed that OOH* and O* intermediates induce variations in the Fe-Fe and Co-Co bond lengths, respectively, suggesting that Fe and Co species are crucial to the ORR/OER processes.

Tuning defects in oxides at room temperature by lithium reduction.

Abstract: Defects can greatly influence the properties of oxide materials; however, facile defect engineering of oxides at room temperature remains challenging. The generation of defects in oxides is difficult to control by conventional chemical reduction methods that usually require high temperatures and are time consuming. Here, we develop a facile room-temperature lithium reduction strategy to implant defects into a series of oxide nanoparticles including titanium dioxide (TiO2), zinc oxide (ZnO), tin dioxide (SnO2), and cerium dioxide (CeO2). Our lithium reduction strategy shows advantages including all-room-temperature processing, controllability, time efficiency, versatility and scalability. As a potential application, the photocatalytic hydrogen evolution performance of defective TiO2 is examined. The hydrogen evolution rate increases up to 41.8 mmol g−1 h−1 under one solar light irradiation, which is ~3 times higher than that of the pristine nanoparticles. The strategy of tuning defect oxides used in this work may be beneficial for many other related applications. Defective oxides are attractive for energy conversion and storage applications, but it remains challenging to implant defects in oxides under mild conditions. Here, the authors develop a versatile lithium reduction strategy to engineer the defects of oxides at room temperature leading to enhanced photocatalytic properties.

A unique oxygen ligand environment facilitates water oxidation in hole-doped IrNiOx core–shell electrocatalysts

Abstract: The electro-oxidation of water to oxygen is expected to play a major role in the development of future electrochemical energy conversion and storage technologies. However, the slow rate of the oxygen evolution reaction remains a key challenge that requires fundamental understanding to facilitate the design of more active and stable electrocatalysts. Here, we probe the local geometric ligand environment and electronic metal states of oxygen-coordinated iridium centres in nickel-leached IrNi@IrOx metal oxide core–shell nanoparticles under catalytic oxygen evolution conditions using operando X-ray absorption spectroscopy, resonant high-energy X-ray diffraction and differential atomic pair correlation analysis. Nickel leaching during catalyst activation generates lattice vacancies, which in turn produce uniquely shortened Ir–O metal ligand bonds and an unusually large number of d-band holes in the iridium oxide shell. Density functional theory calculations show that this increase in the formal iridium oxidation state drives the formation of holes on the oxygen ligands in direct proximity to lattice vacancies. We argue that their electrophilic character renders these oxygen ligands susceptible to nucleophilic acid–base-type O–O bond formation at reduced kinetic barriers, resulting in strongly enhanced reactivities. The precise understanding of the active phase under reaction conditions at the molecular level is crucial for the design of improved catalysts. Now, Strasser, Jones and colleagues correlate the high activity of IrNi@IrOx core–shell nanoparticles with the amount of lattice vacancies produced by the nickel leaching process that takes place before and during water oxidation, and elucidate the underlying structural-electronic effects.

2D Materials for Gas Sensing Applications: A Review on Graphene Oxide, MoS2, WS2 and Phosphorene

Abstract: After the synthesis of graphene, in the first year of this century, a wide research field on two-dimensional materials opens. 2D materials are characterized by an intrinsic high surface to volume ratio, due to their heights of few atoms, and, differently from graphene, which is a semimetal with zero or near zero bandgap, they usually have a semiconductive nature. These two characteristics make them promising candidate for a new generation of gas sensing devices. Graphene oxide, being an intermediate product of graphene fabrication, has been the first graphene-like material studied and used to detect target gases, followed by MoS2, in the first years of 2010s. Along with MoS2, which is now experiencing a new birth, after its use as a lubricant, other sulfides and selenides (like WS2, WSe2, MoSe2, etc.) have been used for the fabrication of nanoelectronic devices and for gas sensing applications. All these materials show a bandgap, tunable with the number of layers. On the other hand, 2D materials constituted by one atomic species have been synthetized, like phosphorene (one layer of black phosphorous), germanene (one atom thick layer of germanium) and silicone (one atom thick layer of silicon). In this paper, a comprehensive review of 2D materials-based gas sensor is reported, mainly focused on the recent developments of graphene oxide, exfoliated MoS2 and WS2 and phosphorene, for gas detection applications. We will report on their use as sensitive materials for conductometric, capacitive and optical gas sensors, the state of the art and future perspectives.

Na+/vacancy disordering promises high-rate Na-ion batteries

Abstract: As one of the most fascinating cathode candidates for Na-ion batteries (NIBs), P2-type Na layered oxides usually exhibit various single-phase domains accompanied by different Na+/vacancy-ordered superstructures, depending on the Na concentration when explored in a limited electrochemical window. Therefore, their Na+ kinetics and cycling stability at high rates are subjected to these superstructures, incurring obvious voltage plateaus in the electrochemical profiles and insufficient battery performance as cathode materials for NIBs. We show that this problem can be effectively diminished by reasonable structure modulation to construct a completely disordered arrangement of Na-vacancy within Na layers. The combined analysis of scanning transmission electron microscopy, ex situ x-ray absorption spectroscopy, and operando x-ray diffraction experiments, coupled with density functional theory calculations, reveals that Na+/vacancy disordering between the transition metal oxide slabs ensures both fast Na mobility (10-10 to 10-9 cm2 s-1) and a low Na diffusion barrier (170 meV) in P2-type compounds. As a consequence, the designed P2-Na2/3Ni1/3Mn1/3Ti1/3O2 displays extra-long cycle life (83.9% capacity retention after 500 cycles at 1 C) and unprecedented rate capability (77.5% of the initial capacity at a high rate of 20 C). These findings open up a new route to precisely design high-rate cathode materials for rechargeable NIBs.

Review on selective hydrogenation of nitroarene by catalytic, photocatalytic and electrocatalytic reactions

Abstract: Selective catalytic hydrogenation of nitroarenes is of great importance for dyestuff and pharmaceutical industry. A critical step toward the rational design of targeted catalysts is to determine their electronic structures and related reaction mechanism. In this review, we summarize the breakthroughs on the development of multiple catalytic technologies in the past decade, including direct hydrogenation using high-pressure hydrogen; transfer hydrogenation using reductive compounds; photocatalytic hydrogenation using hole scavenger; electrocatalytic hydrogenation accompanied with water oxidation. We focus on how to understand the two key element steps including hydrogen dissociation and the activation of nitro group in the process of hydrogenation, and design and fabricate nanostructured catalysts with desired activity and selectivity. For direct catalytic hydrogenation, representative catalysts include metal, metal oxide/sulfide/carbides/nitrides/boride, and functional carbon material, and the crucial factors to tune their activity and selectivity are discussed such as metal-support interaction, size effect, alloy effect, defect engineering, and so on. Catalytic transfer hydrogenation, photocatalytic and electrocatalytic hydrogenation, in which these catalysts abstracts hydrogen species from the hydrogen donor and stabilizes it on the catalyst surface, restricting active H* recombination, and then the active hydrogen species can be promptly transferred to nitroarenes for the hydrogenation. It is worth mentioning that the light harvesting and charge separation of photocatalyst and the conductivity of electrocatalyst should also be considered together for the overall performance. All these experiences lay the foundation for large scale production of anilines and guide the rational design of catalysts for other organic transformation reactions.

A Universal Strategy for Hollow Metal Oxide Nanoparticles Encapsulated into B/N Co-Doped Graphitic Nanotubes as High-Performance Lithium-Ion Battery Anodes

Abstract: Yolk-shell nanostructures have received great attention for boosting the performance of lithium-ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li+ ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co-doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni2 O3 , Mn3 O4 ) through combining pyrolysis with an oxidation method is reported herein. The as-made TMO@BNG exhibits the TMO-dependent lithium-ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium-ion storage capacity of 1554 mA h g-1 at the current density of 96 mA g-1 , good rate ability (410 mA h g-1 at 1.75 A g-1 ), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability.

Metal oxide redox chemistry for chemical looping processes

Abstract: Chemical looping offers a versatile platform to convert fuels and oxidizers in a clean and efficient manner. Central to this technology are metal oxide materials that can oxidize fuels, affording a reduced material that can be reoxidized to close the loop. Recent years have seen substantial advances in the design, formulation and manufacture of these oxygen carrier materials and their incorporation into chemical looping reactors for the production of various chemicals. This Review describes the mechanisms by which oxygen carriers undergo redox reactions and how these carriers can be incorporated into robust chemical looping reactors. One promising technology for modern energy and chemical conversions is chemical looping, central to which are redox cycles of metal oxides. This Review describes chemical looping schemes and the mechanisms by which metal oxide particles enable these technologies.

Modified MXene/Holey Graphene Films for Advanced Supercapacitor Electrodes with Superior Energy Storage

Abstract: MXene films are attractive for advanced supercapacitor electrodes requiring high volumetric energy density due to their high redox capacitance combined with extremely high packing density. However, the self-restacking of MXene flakes unavoidably decreases the volumetric performance, mass loading, and rate capability. Herein, a simple strategy is developed to prepare a flexible and free-standing modified MXene/holey graphene film by filtration of the alkalized MXene and holey graphene oxide dispersions, followed by a mild annealing treatment. After terminal groups (-F/-OH) are removed, the increased proportion of Ti atoms enables more pseudocapacitive reaction. Meanwhile, the embedded holey graphene effectively prevents the self-restacking of MXene and forms a high nanopore connectivity network, which is able to immensely accelerate the ion transport and shorten transport pathways for both ion and electron. When applied as electrode materials for supercapacitors, it can deliver an ultrahigh volumetric capacitance (1445 F cm-3) at 2 mV s-1, excellent rate capability, and high mass loading. In addition, the assembled symmetric supercapacitor demonstrates a fantastic volumetric energy density (38.6 Wh L-1), which is the highest value reported for MXene-based electrodes in aqueous electrolytes. This work opens a new avenue for the further exploration of MXene materials in energy storage devices.

Dendritic core-shell nickel-iron-copper metal/metal oxide electrode for efficient electrocatalytic water oxidation.

Abstract: Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we report a promisingly dendritic core-shell nick ...

Ultrathin graphene oxide encapsulated in uniform MIL-88A(Fe) for enhanced visible light-driven photodegradation of RhB

Abstract: It is very important to design excellent heterojunction structure for the improvement of the photocatalytic performance. In this study, we report a facile approach of polymerizing the ultrathin graphene oxide on the surface of the MIL-88A(Fe) to form MIL-88A(Fe)/grapheme oxide composite for enhancing the photocatalytic efficiency of organic molecules degradation. The optical grapheme oxide doping content in MIL-88A(Fe)/grapheme oxide hybrid is determined to be 9.0 wt%，which increases the surface area of the MOFs from 15.9 m 2 g −1 to 408.9 m 2 g −1 due to the emerging micropores, and the corresponding photocatalytic rate for RhB is 8.4 times higher than that of pure MIL-88A(Fe). Meanwhile, DMF-free MOF-based heterostructure could avoid secondary contamination in the photocatalytic application process, and the degree of RhB removal is maintained at about 100% after the five cycles of the reaction. Integrating the related electrochemical analysis and the active species trapping experiments, the decisive factors for the improved photocatalytic efficiency of MIL-88A(Fe)/grapheme oxide may be the unique structural advantages of ultrathin grapheme oxide sheets, compact and uniform interface contact, more adsorption sites and more reaction sites. This work provides a novel sight for preparing high-efficient and environment-stable photocatalysts by designing the surface heterojunction structure.

A high-energy-density lithium-oxygen battery based on a reversible four-electron conversion to lithium oxide

Abstract: Lithium-oxygen (Li-O 2 ) batteries have attracted much attention owing to the high theoretical energy density afforded by the two-electron reduction of O 2 to lithium peroxide (Li 2 O 2 ). We report an inorganic-electrolyte Li-O 2 cell that cycles at an elevated temperature via highly reversible four-electron redox to form crystalline lithium oxide (Li 2 O). It relies on a bifunctional metal oxide host that catalyzes O–O bond cleavage on discharge, yielding a high capacity of 11 milliampere-hours per square centimeter, and O 2 evolution on charge with very low overpotential. Online mass spectrometry and chemical quantification confirm that oxidation of Li 2 O involves transfer of exactly 4 e – /O 2 . This work shows that Li-O 2 electrochemistry is not intrinsically limited once problems of electrolyte, superoxide, and cathode host are overcome and that coulombic efficiency close to 100% can be achieved.

O2 Activation by Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous Catalysts

Abstract: The activation of O2 on metal surfaces is a critical process for heterogeneous catalysis and materials oxidation. Fundamental studies of well-defined metal surfaces using a variety of techniques have given crucial insight into the mechanisms, energetics, and dynamics of O2 adsorption and dissociation. Here, trends in the activation of O2 on transition metal surfaces are discussed, and various O2 adsorption states are described in terms of both electronic structure and geometry. The mechanism and dynamics of O2 dissociation are also reviewed, including the importance of the spin transition. The reactivity of O2 and O toward reactant molecules is also briefly discussed in the context of catalysis. The reactivity of a surface toward O2 generally correlates with the adsorption strength of O, the tendency to oxidize, and the heat of formation of the oxide. Periodic trends can be rationalized in terms of attractive and repulsive interactions with the d-band, such that inert metals tend to feature a full d band ...

Composite of CH3NH3PbI3 with Reduced Graphene Oxide as a Highly Efficient and Stable Visible-Light Photocatalyst for Hydrogen Evolution in Aqueous HI Solution

Abstract: A facile and efficient photoreduction method is employed to synthesize the composite of methylammonium lead iodide perovskite (MAPbI3 ) with reduced graphene oxide (rGO). This MAPbI3 /rGO composite is shown to be an outstanding visible-light photocatalyst for H2 evolution in aqueous HI solution saturated with MAPbI3 . Powder samples of MAPbI3 /rGO (100 mg) show a H2 evolution rate of 93.9 µmol h-1 , which is 67 times faster than that of pristine MAPbI3 , under 120 mW cm-2 visible-light (λ ≥ 420 nm) illumination, and the composite is highly stable showing no significant decrease in the catalytic activity after 200 h (i.e., 20 cycles) of repeated H2 evolution experiments. The electrochemiluminescence performance of MAPbI3 is investigated to explore the charge transfer process, to find that the photogenerated electrons in MAPbI3 are transferred to the rGO sites, where protons are reduced to H2 .