NiFe LDH-CoPc/CNTs as novel bifunctional electrocatalyst complex for zinc–air battery

A new type of composite electrocatalyst was designed and prepared with NiFe layered double hydroxides (LDHs) for oxygen evolution reaction (OER) and CoPc for oxygen reduction reaction (ORR) supported on carbon nanotubes (CNTs). The NiFe LDH–CoPc/CNT composite exhibits higher electrocatalytic activity and stability than the commercial precious metal catalyst Pd/C + Ru/C in 6 M KOH electrolyte. The resulting rechargeable Zn–air battery showed high discharge voltage at 195 mW cm^?2. The discharge voltage is around 1.08~0.95 V and the charge voltage is lower, 2.07 V, after the cycle of 300 h at 80 mA cm^?2, indicating that zinc–air battery possessed high reversibility and durability over long charge and discharge cycles.     

Co3O4 Hollow Nanoparticles and Co Organic Complexes Highly Dispersed on N‐Doped Graphene: An Efficient Cathode Catalyst for Li‐O2 Batteries

Rechargeable Li‐O₂ batteries are promising candidates for electric vehicles due to their high energy density. However, the current development of Li‐O₂ batteries demands highly efficient air cathode catalysts for high capacity, good rate capability, and long cycle life. In this work, a hydrothermal‐calcination method is presented to prepare a composite of Co₃O₄ hollow nanoparticles and Co organic complexes highly dispersed on N‐doped graphene (Co–NG), which acts as a bifunctional air cathode catalyst to optimize the electrochemical performances of Li‐O₂ batteries. Co–NG exhibits an outstanding initial discharge capacity up to 19 133 mAh g^?1 at a current density of 200 mA g^?1. In addition, the batteries could sustain 71 cycles at a cutoff capacity of 1000 mAh g^?1 with low overpotentials at the current density of 200 mA g^?1. Co–NG composites are attractive as air cathode catalysts for rechargeable Li‐O₂ batteries.     

Co3O4 Hollow Polyhedrons as Bifunctional Electrocatalysts for Reduction and Evolution Reactions of Oxygen

It is very important to exploit low‐cost and efficient oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts for the development of renewable‐energy conversion and storage techniques. Although much attention has been made to develop efficient catalysts for ORR and OER, it is still highly desired to create new bifunctional catalysts. In this study, Co₃O₄ hollow polyhedrons are synthesized as efficient bifunctional electrocatalysts for ORR and OER by simple one‐step annealing Co‐centered metal–organic frameworks (ZIF‐67). Due to the large specific surface areas and high porosity, the as‐prepared Co₃O₄ hollow polyhedrons exhibit excellent electrocatalytic activities for ORR and OER in alkaline media. Co₃O₄ hollow polyhedrons show higher peak current density (0.61 mA cm^?2) with four‐electron pathway than Co₃O₄ particles (0.39 mA cm^?2), better methanol tolerance and superior durability (82.6%) than commercial Pt/C electrocatalyst (58.6%) for ORR after 25 000 s. In addition, Co₃O₄ hollow polyhedrons also display excellent OER performances with smaller overpotential (536 mV) for 10 mA cm^?2 than Co₃O₄ particles (593 mV) and superior stability (86.5%) after 25 000 s. This facile one‐step strategy based on metal–organic frameworks self‐sacrificed templates can be used to develop the promising well‐defined porous hollow metal oxides electrode materials for energy conversion and storage technologies.     

Co3O4@Co Nanoparticles Embedded Porous N‐Rich Carbon Matrix for Efficient Oxygen Reduction

Oxygen reduction reaction (ORR) is an important reaction in many energy conversion systems, but it is severely restricted by its slow kinetics. Developing efficient non‐noble‐metal catalysts for ORR has attracted extended interests, but still remains a great challenge. Herein, an efficient catalysts consisting of Co₃O₄@Co nanoparticles embedded in N‐rich mesoporous carbon matrix is developed by the carbonization of Co‐containing zeolitic imidazolate framework precursor. The derived matrix exhibits outstanding catalytic activity with onset potential of 0.97 V vs. RHE, half‐wave potential of 0.88 V vs. RHE, and good catalytic durability when tested with the rotation speed of 1600 rpm. Carbinization under NH₃ introduces extra elemental N, which subsequently enhances the limiting current densities. This study provides insight into the rational design of highly active ORR catalysts.     

Electrocatalytically Active Hollow Carbon Nanospheres Derived from PS‐b‐P4VP Micelles

A facile method using polystyrene‐b‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) micelles is demonstrated to synthesize N/FeN₄‐doped hollow carbon nanospheres (N/FeN₄‐CHNS) with high electrocatalytic activity for oxygen reduction reactions (ORRs). Uniform spherical micelles with PS core and P4VP shell are prepared by exposing PS‐b‐P4VP in a mixture of ethanol/tetrahydrofuran. Pyridinic N in shell cooperates with Fe³⁺ to induce an in situ polymerization of pyrrole. Tuning molecular composition of PS‐b‐P4VP can form hollow carbon spheres with controlled size down to sub‐100 nm that remains challenge using traditional hard template strategies. N/FeN₄‐CHNS possesses a series of desirable properties as electrode materials, including easy fabrication, high reproducibility, large surface area, and highly accessible porous surface. This electrocatalyst exhibits excellent ORR activity (onset potential of 0.976 V vs reversible hydrogen electrode (RHE) and half‐wave potential of 0.852 V vs RHE), higher than that of commercial Pt/C (20 wt%) in an alkaline media, and shows a good activity in an acidic media as well. In addition to its higher stability and methanol tolerance than Pt/C in both alkaline and acidic electrolytes, highly competitive single cell performance is achieved in a proton exchange membrane fuel cell. This work provides a general approach to preparing functionalized small hollow nanospheres based on self‐assembly of block copolymers.     

Anodic TiO2 nanotubes as anode electrode in Li–air and Li-ion batteries

We investigate the possibility of using a TiO₂ anode as an alternative to the Li electrode in Li–air and Li-ion rechargeable batteries. TiO₂ nanotube layer is fabricated by the anodization method and optional thermal treatment is conducted. The electrochemical charge/discharge profile of the TiO₂/liquid electrolyte/LiCoO₂ structured cell is measured under the flowing of O₂, N₂ and Ar, respectively. The elevation of the upper cut-off voltage from 3 to 4.5 V leads to an increase in the specific capacity by a factor of more than three. We suppose this to be a novel mechanism in which the TiO₂/LiCoO₂ system under the oxygen atmosphere works in Li–air battery mode up to 3 V and then works in Li-ion battery mode from 3 V to 4.5 V. This idea is confirmed by ICP-OES analysis.     

A Dual Component Catalytic System Composed of Non‐Noble Metal Oxides for Li–O2 Batteries with Enhanced Cyclability

One of the great challenges in the development of lithium–oxygen batteries (Li–O₂ batteries) is to synthesize cost‐effective and efficient electrocatalysts to overcome several issues such as high charge overpotential and poor cycle life. Here, an efficient method is reported to fabricate a dual component electrocatalyst made of MnO₂ nanoparticles supported on 1D Co₃O₄ nanorods (MnO₂–Co₃O₄), and its electrochemical behavior as a non‐noble metal cathode catalyst is demonstrated in Li–O₂ batteries. It is found that the as‐made MnO₂–Co₃O₄ catalyst exhibits an enhanced electrochemical performance, such as increased specific capacity (increase to 4023 mA h g^?1 from 2993 mA h g^?1), low charge overpotential (reduce 350 mV), high rate performance, and superior cyclability up to 150 cycles. The excellent electrochemical performance is attributed to the synergistic effects of the dual component catalytic system.     

Optimization of rechargeable zinc-air battery with Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/MnO<Subscript>2</Subscript>/CNT bifunctional catalyst: effects of catalyst loading,binder content,and spraying area

The air cathode is the most crucial component for a zinc-air battery (ZAB) system, which inquires fast diffusion of gaseous O₂ and decent bifunctional catalytic performance. Herein, based on our previous attempts, we developed a bi-functional electro-catalyst utilizing co-doped manganese dioxide nanotube/carbon nanotube (CNT) composite to improve the catalytic activity toward both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A simple characterization of the morphology and physicochemical properties of various Co₃O₄/MnO₂/CNT (CMC) composites was performed by employing various techniques (SEM, TEM, and XRD). More importantly, using CMC composite as the bifunctional cathode catalysts, we thoroughly investigated the effects of catalyst loading, bonding layer loading, and spraying area in catalyst layer (CL) on cell performance and charge-discharge cyclic ability for rechargeable zinc-air batteries. The highest peak power density of 400.3 mW cm^?2 can be reached when the catalyst loading is 3 mg cm^?2, the spraying area is 1 cm² and the binder content is 80 μL. The rechargeable zinc-air batteries with the air electrodes containing different spraying areas and bonding layer loadings are stably operated for 22 h at a high current density (100 mA cm^?2) and show a maximum voltage gap of 1.5 V between charge and discharge voltages. All these optimization efforts are particularly important to future large-scale applications in ZAB.

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Intramolecular Diels–Alder reaction in enyne–allenes: a computational investigation and comparison with the Myers–Saito and Schmittel reactions

The reaction mechanisms as well as substituted effect and solvent effect of the enyne–allenes are investigated by Density Functional Theory (DFT) method and compared with the Myers–Saito and Schmittel reactions. The Myers–Saito reaction of non‐substituted enyne–allenes is kinetically and thermodynamically favored as compared to the Schmittel reaction; while the concerted [4 + 2] cycloaddition is only 1.32 kcal/mol higher than the C₂? C₇ cyclization and more exothermic (Δ_RE = ?69.38 kcal/mol). For R₁ = CH₃ and t‐Bu, the increasing barrier of the C₂? C₇ cyclization is higher than that for the C₂? C₆ cyclization because of the steric effect, so the increased barrier of the [4 + 2] cycloaddition is affected by such substituted electron‐releasing group. Moreover, the strong steric effect of R₁ = t‐Bu would shift the C₂? C₇ cyclization to the [4 + 2] cycloaddition. On the other hand, for R₁ = Ph, NH₂, O^?, NO₂, and CN substituents, the barrier of the C₂? C₆ cyclization would be more diminished than the C₂? C₇ cyclization due to strong mesomeric effect; the reaction path of C₂? C₇ cyclization would also shift to the [4 + 2] cycloaddition. The solvation does not lead to significant changes in the potential‐energy surface of the reaction except for the more polar surrounding solvent such as dimethyl sulfoxide (DMSO), or water. Copyright © 2009 John Wiley & Sons, Ltd.     

MFe2O4 and MFe@Oxide Core–Shell Nanoparticles Anchored on N‐Doped Graphene Sheets for Synergistically Enhancing Lithium Storage Performance and Electrocatalytic Activity for Oxygen Reduction Reactions

The intrinsically low electric conductivity and self‐aggregation of MFe₂O₄ during charge/discharge affect their lithium storage performance and electrocatalytic activity. To mitigate these problems, it is shown that N‐doped graphene sheets (NGS), as a highly conductive platform, finely disperse the MFe₂O₄ nanoparticles and rapidly shuttle electrons to and from the MFe₂O₄ nanoparticles. Moreover, by forming a metal@oxide core–shell nanostructure, fast electron transfer from the exterior oxide layer to NGS is achieved. Introducing NGS into MFe₂O₄ allows the composites to exhibit the comparable specific capacity (based on the total mass) to MFe₂O₄, although over 10 wt% of NGS contributes a low specific capacity of around 320–400 mAh g^?1. More importantly, introducing NGS significantly increases the cycling stability performance: 97.5% (CoFe₂O₄/NGS) and ≈100% (NiFe₂O₄/NGS) of the specific capacities have been retained after 80 cycles, far higher than the capacity retentions of CoFe₂O₄ (35.3%) and NiFe₂O₄ (43.7%) tested under otherwise identical conditions. Also demonstrated are the excellent rate capabilities of the composites. For catalyzing the oxygen reduction reaction, the activity is significantly improved when the MFe₂O₄ nanoparticles are transformed into metal@oxide core–shell nanostructure, mainly because the core–shell nanostructure exhibits lower charge transfer resistance.