Synthetic Molecular Rectifier of a Langmuir–Blodgett Film Based on a Novel Asymmetrically Substituted Dicyano‐tri‐tert‐butylphthalocyanine

A novel asymmetrically substituted dicyano‐tri‐tert‐butylphthalocyanine ((CN)₂BuPc) with rectifying behavior has been synthesized. The morphology and conductive properties of (CN)₂BuPc Langmuir–Blodgett (LB) films on mica and highly ordered pyrolytic graphite (HOPG) substrates were studied by atomic force microscopy (AFM) and scanning tunneling microscopy (STM), in air at 22 °C. The average area of each (CN)₂BuPc molecule obtained from the AFM topography in situ is ca. 73.6 Ų, which is in good agreement with the result of ca. 74 Ų obtained from the π–A isotherm curve of a LB film. This indicates that the molecules are standing edge‐on, tilted by 38° against the surface normal of the substrate. The conductive properties for the 7‐layer LB films of (CN)₂BuPc were studied by STM with a tungsten tip. The asymmetric I–V curve revealed a type of rectifying behavior for a negative and a positive bias. A feature model of the intramolecular and intermolecular charge transfer is presented. It not only interprets electron transfer from electron‐donor to electron‐acceptor molecules via a molecular “bridge”, but also the tunneling effect through intermolecular charge transfer.     

Cover Picture: Bilayer Organic–Inorganic Gate Dielectrics for High‐Performance,Low‐Voltage,Single‐Walled Carbon Nanotube Thin‐Film Transistors,Complementary Logic Gates,and p–n Diodes on Plastic Substrates (Adv. Funct. Mater. 18/2006)

Low‐voltage, hysteresis‐free, flexible thin‐film‐type electronic systems based on networks of single‐walled carbon nanotubes and bilayer organic–inorganic nanodielectrics are detailed in work by Rogers and co‐workers reported on p. 2355. The cover image shows a schematic array of such thin‐film transistors (TFTs) on a plastic substrate. The structure of the bilayer nanodielectric, which consists of a film of HfO₂ formed by atomic layer deposition and an ultrathin layer of epoxy formed by spin‐casting, is also illustrated schematically. High‐capacitance bilayer dielectrics based on atomic‐layer‐deposited HfO₂ and spin‐cast epoxy are used with networks of single‐walled carbon nanotubes (SWNTs) to enable low‐voltage, hysteresis‐free, and high‐performance thin‐film transistors (TFTs) on silicon and flexible plastic substrates. These HfO₂–epoxy dielectrics exhibit excellent properties including mechanical flexibility, large capacitance (up to ca. 330 nF cm^–2), and low leakage current (ca. 10^–8 A cm^–2); their low‐temperature (ca. 150 °C) deposition makes them compatible with a range of plastic substrates. Analysis and measurements of these dielectrics as gate insulators in SWNT TFTs illustrate several attractive characteristics for this application. Their compatibility with polymers used for charge‐transfer doping of SWNTs is also demonstrated through the fabrication of n‐channel SWNT TFTs, low‐voltage p–n diodes, and complementary logic gates.     

Bilayer Organic–Inorganic Gate Dielectrics for High‐Performance,Low‐Voltage,Single‐Walled Carbon Nanotube Thin‐Film Transistors,Complementary Logic Gates,and p–n Diodes on Plastic Substrates

High‐capacitance bilayer dielectrics based on atomic‐layer‐deposited HfO₂ and spin‐cast epoxy are used with networks of single‐walled carbon nanotubes (SWNTs) to enable low‐voltage, hysteresis‐free, and high‐performance thin‐film transistors (TFTs) on silicon and flexible plastic substrates. These HfO₂–epoxy dielectrics exhibit excellent properties including mechanical flexibility, large capacitance (up to ca. 330 nF cm^–2), and low leakage current (ca. 10^–8 A cm^–2); their low‐temperature (ca. 150 °C) deposition makes them compatible with a range of plastic substrates. Analysis and measurements of these dielectrics as gate insulators in SWNT TFTs illustrate several attractive characteristics for this application. Their compatibility with polymers used for charge‐transfer doping of SWNTs is also demonstrated through the fabrication of n‐channel SWNT TFTs, low‐voltage p–n diodes, and complementary logic gates.     

Highly Conductive,Bendable, Embedded Ag Nanoparticle Wire Arrays Via Convective Self‐Assembly: Hybridization into Ag Nanowire Transparent Conductors

The optoelectrical properties of Ag nanowire (NW) networks are improved by incorporating the NWs into highly conductive ordered arrays of Ag nanoparticle wires (NPWs) fabricated via surfactant‐assisted convective self‐assembly. The NPW–NW hybrid conductor displays a transmittance (T) of 90% at 550 nm and a sheet resistance (R _s) of 5.7 Ω sq^?1, which is superior to the corresponding properties of the NW network showing a R _s of 14.1 Ω sq^?1 at a similar T. By the modified wettability of a donor substrate and the capillarity of water, the sintered NPW–NW hybrid conductors are perfectly transferred onto an UV‐curable photopolymer film, and the embedded hybrid conductors exhibit excellent electromechanical properties. The R _s and T of the NPW arrays can be predicted by using a simple model developed to calculate the width and height of the hexagonal close‐packed particles formed during the convective self‐assembly. The numerical analysis reveals that the maximum Haacke figure of merit of the NW networks is increased considerably from 0.0260 to 0.0407 Ω^?1 by integration with the NPW array. The highly conductive NPW arrays generated using a simple, low‐cost, and nonlithographic process can be applied to enhancing the performances of other transparent conductors, such as carbon nanotubes, metal oxides, and graphenes.     

The Relationship between Structural and Electrical Characteristics in Perylenecarboxydiimide‐Based Nanoarchitectures

The controlled assembly of the prototypical n‐type organic semiconductor N,N′‐1H,1H‐perfluorobutyl dicyanoperylenecarboxydiimide (PDIF‐CN₂) into ordered nanoarchitectures and the multiscale analysis of the correlation between their structural and their electrical properties is reported. By making use of the Langmuir–Blodgett (LB) technique, monolayers of PDIF‐CN₂ arranged in upright standing molecular packing on different substrates are formed. Postdeposition thermal treatment makes it possible to trigger a reorganization into layered ultrathin crystalline nanostructures, exhibiting structural and photophysical properties similar to those of microscopic crystals obtained by solvent‐induced precipitation. The controlled engineering of these molecular architectures on surfaces enables us to identify both a dependence of the monolayer resistance on the molecular tilt angle in vertical junctions and a pronounced charge‐transport anisotropy with enhanced transport along the π–π stacking direction of the PDI core. While a charge carrier mobility for electrons as high as 10^–2 cm² V^–1 s^–1 is determined in monolayer field‐effect transistors for the in‐plane direction, being the highest yet reported value for a n‐type LB monolayer, the out‐of‐plane mobility measured by conductive atomic force microscopy in multilayered structures is found to be one order of magnitude lower.     

AFM and TEM observations of alpha-helix to beta-sheet conformational change occurring on carbon nanotubes

Bacteriorhodopsin (BR), which is rich in alpha-helical structure, was spread onto water with single-wall carbon nanotubes (SCNTs). After a Langmuir trough was used to apply compressive surface pressure to maintain the alpha-helices monolayer of denatured BR, the composite films comprising alpha-helices and SCNTs were transferred horizontally onto substrates. Atomic force microscopy (AFM) and fluorescence microscopy observation suggested that alpha-helices in contact with SCNTs changed into beta-sheets. High-resolution transmission electron microscopy (HR-TEM) showed 0.54 nm periodicity characteristic of the turn of alpha-helical structure in the SCNTs-free alpha-helix monolayer region and showed the 0.70 nm periodicity of beta-sheet pleated structure in the region where SCNTs were covered with unfolded BR. Unique features of carbon nanotubes that trigger conformational changes of a protein were revealed.     

Organic Thin‐Film Transistors Based on Tolyl‐Substituted Oligothiophenes

Thin films based on the tolyl‐substituted oligothiophenes 5,5′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′‐terthiophene ( 1 ), 5,5′′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′:5′′,2′′′‐quaterthiophene ( 2 ) and 5,5′′′′‐bis(4‐methylphenyl)‐2,2′:5′,2′′:5′′,2′′′:5′′′,2′′′′‐quinqethiophene ( 3 ) exhibit hole‐transport behavior in a thin‐film transistor (TFT) configuration, with reasonable mobilities and high current on/off (I_on/I_off) ratios. Powder X‐ray diffraction (PXRD) reveals that these films, grown by vacuum deposition onto the thermally grown silicon oxide surface of a TFT, are highly crystalline, a characteristic that can be attributed to the general tendency of phenyl groups to promote crystallinity. Atomic force microscopy (AFM) reveals that the films grow layer by layer to form large domains, with some basal domain areas approaching 1000 μm². The PXRD and AFM data are consistent with an “end‐on” orientation of the molecules on the oxide substrate. Variable‐temperature current–voltage (I–V) measurements identified the activation regime for hole transport and revealed shallow level traps in thin films of 1 and 2 , and both shallow and deep level traps in thin films of 3 . The activation energies for thin films of 1 , 2 , and 3 were similar, with values of E_a = 121, 100, and 109 meV, respectively. The corresponding trap densities were N_trap/N_v = 0.012, 0.023, and 0.094, where N_trap is the number of trap states and N_v is the number of conduction states. The hole mobilities for the three compounds were similar (μ ? 0.03 cm² V^–1 s^–1), and the I_on/I_off ratios were comparable with the highest values reported for organic TFTs, with films of 2 approaching I_on/I_off = 10⁹ at room temperature.     

Dye‐sensitized TiO2 solar cells based on nanocomposite photoanode containing plasma‐modified multi‐walled carbon nanotubes

A series of anatase TiO₂‐based nanocomposite incorporated with plasma‐modified multi‐walled carbon nanotubes (MWNTs) was prepared by physical blending and shows its capability for efficient electron transport when used as photoanode in dye‐sensitized solar cells (DSSCs). These MWNTs characterized with good dispersal performance were obtained by functionalization technique via in situ plasma treatment and subsequent grafting with maleic anhydride (MA) onto the external walls reported previously. Compared with the conventional DSSCs, the TiO₂ film with 1D carbon nanotubes possesses more outstanding ability to transport electrons injected from the excited dye within the device under illumination. As a result, at an optimum addition of 0.3 wt% MWNTs‐MA in TiO₂ matrix, the photocurrent–voltage (J–V) characteristics showed a significant increase in the short‐circuit photocurrent (J_sc) of 50%, leading to an increase in overall solar conversion efficiency by a factor of 1.5. Electrochemical impedance spectroscopy analyses reveal that the MWNTs‐MA/TiO₂ incur smaller resistances at the photoanode in assembled DSSCs when compared with those in the anatase titania DSSCs. These features suggest that the conducting properties of the MWNTs‐MA within the anodes are crucial for achieving a higher transport rate for photo‐induced electrons in TiO₂ layer by exhibiting lower resistance in the porous network and hence retard charge recombination that could result in poor conversion efficiency. Copyright © 2012 John Wiley & Sons, Ltd.     

Hydrophilic Nanotube Supported Graphene–Water Dispersible Carbon Superstructure with Excellent Conductivity

In this work, it is shown that the hydrophilic functionalized multiwall carbon nanotubes (MWCNs) can stabilize a large amount of pristine graphene nanosheets in pure water without the assistance of surfactants, ionic liquids, or hydrophilic polymers. Role of stabilizer is conveyed by highly hydrophilic carbon nanotubes, functionalized by dihydroxy phenyl groups, affording a stable dispersion at concentrations as high as 15 mg mL^?1. Such multidimensional (2D/1D) graphene/MWCN hybrid is found to be dispersible also in other polar organic solvents such as ethanol, isopropanol, N,N‐dimethylformamide, ethylene glycol, and their mixtures. High‐resolution transmission microscopy and atomic force microscopy (AFM) including a liquid mode AFM manifest several types of interaction including trapping of multiwalled carbon nanotubes between the graphene sheets or the modification of graphene edges. Molecular dynamic simulations show that formation of an assembly is kinetically controlled. Importantly, the hybrid can be deposited on the paper by drop casting or dispersed in water‐soluble polymers resulting in record values of electrical conductivity (sheet resistance up to R_s ≈ 25 Ω sq^?1 for free hybrid material and R_s ≈ 1300 Ω sq^?1 for a polyvinilalcohol/hybrid composite film). Thus, these novel water dispersible carbon superstructures reveal a high application potential as conductive inks for inkjet printing or as highly conductive polymers.     

UV‐Light‐Driven Immobilization of Surface‐Functionalized Oxide Nanocrystals onto Silicon

TiO₂ nanorods (NRs) and γ‐Fe₂O₃ nanocrystals (NCs) passivated with unsaturated long‐chain carboxylic acids, namely 10‐undecylenic acid (10UDA) and oleic acid (OLEA), are covalently anchored to Si(100) at room temperature by UV‐light‐driven reaction of hydrogenated silicon with the carbon–carbon double bond (–C?C–) moieties of the capping surfactants. The high reactivity of vinyl groups towards Si provides a general tool for attaching particles of both materials via Si–C bonds. Interestingly, TiO₂ NRs were efficiently attached to silicon even when capped by OLEA. This latter finding has been explained by a photocatalytic mechanism involving the primary role of hydroxyl radicals that can be generated upon bandgap TiO₂ photoexcitation with UV light. The increased oxide coverage achievable on Si opens access to further surface manipulation, as demonstrated by the possibility of depositing an additional film of Au nanoparticles onto TiO₂ via TiO₂‐catalyzed visible‐light‐driven reduction of aqueous AuCl₄^– ions. Extensive morphological and chemical characterization of the obtained NC‐functionalized Si substrates is provided to support the effectiveness of proposed photochemical approaches.     

Studies of multiple-chain alkylaminomethyl p-cyanophenol derivatives for Langmuir–Blodgett films

Langmuir films and Langmuir–Blodgett deposition have been studied for 2,6-dioctadecyl-aminomethyl-4-cyanophenol (CPR₂R₂) and 2-dioctadecyl-aminomethyl-4-cyanophenol (CPR₂). Stable Langmuir films were obtainable for both compounds at high pH, but only for CPR₂R₂ at low pH. Molecular modelling and semiempirical MNDO calculations suggest that high pH favours stability by disrupting intramolecular hydrogen bonding. X-ray diffraction on Y-type Langmuir–Blodgett films deposited on hydrophobic glass substrates gives layer spacings of about 56 A3 for both compounds, indicating that the alkyl chains orient perpendicular to the substrate. Modelling and MNDO calculations suggest that analogous compounds with a single octadecyl chain on nitrogen could be stable at both low and high pH. © 1997 John Wiley & Sons, Ltd.     

Tuning and Enhancing Photoluminescence of Light‐Emitting Polymer Nanotubes through Electron‐Beam Irradiation

A new method for the tuning and enhancing photoluminescence (PL) characteristics of light emitting poly (3‐methylthiopnehe) (P3MT) nanotubes through E‐beam irradiation under atmospheric environments is reported. An E‐beam generated from a linear electron accelerator (1 MeV, 1.6 × 10¹³–8.0 × 10¹⁶ electrons cm^–2) is irradiated onto P3MT nanotubes including an Al₂O₃ template. From laser confocal microscope (LCM) PL experiments, significant enhancements in the PL intensity—up to about 90 times of an isolated single strand of the E‐beam irradiated P3MT nanotubes—are observed. The luminescent color of the P3MT nanotubes changes from green to red color depending on the variation of E‐beam dosage. These results might originate from the de‐doping effect and the conformational modification through E‐beam irradiations. Conformational changes of the E‐beam irradiated P3MT nanotubes are confirmed by LCM single Raman and ultraviolet‐visible (UV/Vis) absorption spectra. From UV/Vis absorption spectra, it is observed that the π–π* transition peak and the doping induced bipolaron peaks of the P3MT nanotubes dramatically vary with E‐beam irradiating conditions.     

Influence of Molecular Weight on the Surface Morphology of Aligned,Branched Side‐Chain Polyfluorene

The surface structure of uniaxially aligned poly(9,9‐bis(ethylhexyl)‐fluorene‐2,7‐diyl) films on rubbed polyimide has been studied as a function of molecular weight (M_n = 3–150 kg mol^–1, number‐average molecular weight) using polarized microscopy, atomic force microscopy (AFM), X‐ray reflectivity, and grazing‐incidence X‐ray diffraction. At the threshold M_n, M_n* = 10⁴ g mol^–1, there is a prominent transition in morphology from featureless (M_n < M_n*) to rough (M_n > M_n*), corresponding to the nematic–hexagonal phase transition. The hexagonal phase reveals two coexistent crystallite types in the whole film and at least one crystallite type has been observed at the surface by AFM. The combined optimization of alignment and surface smoothness is achieved slightly below M_n* while the combined optimization of orientational and local order and moderately smooth surface is achieved slightly above M_n*.     

The Remarkable Thermal Stability of Amorphous In‐Zn‐O Transparent Conductors

Transparent conducting oxides (TCOs) are increasingly critical components in photovoltaic cells, low‐e windows, flat panel displays, electrochromic devices, and flexible electronics. The conventional TCOs, such as Sn‐doped In₂O₃, are crystalline single phase materials. Here, we report on In‐Zn‐O (IZO), a compositionally tunable amorphous TCO with some significantly improved properties. Compositionally graded thin film samples were deposited by co‐sputtering from separate In₂O₃ and ZnO targets onto glass substrates at 100 °C. For the metals composition range of 55–84 cation% indium, the as‐deposited IZO thin films are amorphous, smooth (R_RMS < 0.4 nm), conductive (σ ∼ 3000 Ω⁻¹ · cm⁻¹), and transparent in the visible (T_Vis > 90%). Furthermore, the amorphous IZO thin films demonstrate remarkable functional and structural stability with respect to heating up to 600 °C in either air or argon. Hence, though not completely understood at present, these amorphous materials constitute a new class of fundamentally interesting and technologically important high performance transparent conductors.     

Photo‐Induced Functionalization of Spherical and Planar Surfaces via Caged Thioaldehyde End‐Functional Polymers

The synthesis and application of a novel reversible addition‐fragmentation chain transfer (RAFT) agent carrying a photocaged thioaldehyde moiety is described (λ_max = 355 nm). RAFT polymerization of styrene, dimethylacrylamide and a glycomonomer is evidenced (3600 g mol^?1 ≤ M_n ≤ 15 000 g mol^?1; 1.07 ≤ ? ≤ 1.20) with excellent end‐group fidelity. The photogenerated thioaldehyde on the chain ends can undergo hetero Diels–Alder reactions with dienes as well as reactions with nucleophiles. The terminal photoreactive polymers are photografted to porous diene‐reactive polymeric microspheres. The grafted particles are in‐depth characterized via scanning electron microscopy, elemental analysis, X‐ray photoelectron spectroscopy, and high resolution FT‐IR microscopy, leading to a qualitative as well as quantitative image of the core–shell objects. Grafting densities up to 0.10 molecules nm^?2 are reached. The versatility of the thioaldehyde ligation is evidenced by spatially resolved grafting of polystyrene onto nucleophilic groups present in poly (dopamine) (PDA)‐coated glass slides and silicon wafers via two‐photon direct laser writing (DLW) imaged by ToF‐SIMS. The combination of thioaldehyde ligation, RAFT polymerization, and DLW allows for the spatially resolved grafting of a vast range of polymers onto various substrates in any desired pattern with sub‐micrometer resolution.     

Self‐Assembling Nanotubes Consisting of Rigid Cyclic γ‐Peptides

Self‐assembling cyclic peptide nanotubes (SPNs) have been extensively studied due to their potential applications in biology and material sciences. Cyclic γ‐peptides, which have a larger conformational space, have received less attention than the cyclic α‐ and β‐peptides. The self‐assembly of cyclic homo‐γ‐tetrapeptide based on cis‐3‐aminocyclohexanecarboxylic acid (γ‐Ach) residues, which can be easily synthesized by a one‐pot process is investigated. Fourier transform infrared (FTIR) and NMR analysis along with density functional theory (DFT) calculations indicate that the cyclic homo‐γ‐tetrapeptide, with a non‐planar conformation, can self‐assemble into nanotubes through hydrogen‐bond‐mediated parallel stacking. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) experiments reveal the formation of bundles of nanotubes in CH₂Cl₂/hexane, but individual nanotubes and bundles of only two nanotubes are obtained in water. The integration of TEG (triethylene glycol) monomethyl ether chains and cyclopeptide backbones may allow the control of width of single nanotubes.     

Gas Sensing of NiO‐SCCNT Core–Shell Heterostructures: Optimization by Radial Modulation of the Hole‐Accumulation Layer

Hierarchical core–shell (C–S) heterostructures composed of a NiO shell deposited onto stacked‐cup carbon nanotubes (SCCNTs) are synthesized by atomic layer deposition (ALD). A film of NiO particles (0.80–21.8 nm in thickness) is uniformly deposited onto the inner and outer walls of the SCCNTs. The electrical resistance of the samples is found to increase of many orders of magnitude with the increasing of the NiO thickness. The response of NiO–SCCNT sensors toward low concentrations of acetone and ethanol at 200 °C is studied. The sensing mechanism is based on the modulation of the hole‐accumulation region in the NiO shell layer upon chemisorption of the reducing gas molecules. The electrical conduction mechanism is further studied by the incorporation of an Al₂O₃ dielectric layer at NiO and SCCNT interfaces. The investigations on NiO–Al₂O₃–SCCNT, Al₂O₃–SCCNT, and NiO–SCCNT coaxial heterostructures reveal that the sensing mechanism is strictly related to the NiO shell layer. The remarkable performance of the NiO–SCCNT sensors toward acetone and ethanol benefits from the conformal coating by ALD, large surface area of the SCCNTs, and the optimized p‐NiO shell layer thickness followed by the radial modulation of the space‐charge region.     

Ultrathin PECVD epitaxial Si solar cells on glass via low‐temperature transfer process

Fabrication of high‐quality ultrathin monocrystalline silicon layers and their transfer to low‐cost substrates are key steps for flexible electronics and photovoltaics. In this work, we demonstrate a low‐temperature and low‐cost process for ultrathin silicon solar cells. By using standard plasma‐enhanced chemical vapor deposition (PECVD), we grow high‐quality epitaxial silicon layers (epi‐PECVD) from SiH₄/H₂ gas mixtures at 175 °C. Using secondary ion mass spectrometry and transmission electron microscopy, we show that the porosity of the epi‐PECVD/crystalline silicon interface can be tuned by controlling the hydrogen accumulation there. Moreover, we demonstrate that 13–14% porosity is a threshold above which the interface becomes fragile and can easily be cleaved. Taking advantage of the H‐rich interface fragility, we demonstrate the transfer of large areas (∽10 cm²) ultrathin epi‐PECVD layers (0.5–5.5 µm) onto glass substrates by anodic bonding and moderate annealing (275–350 °C). The structural properties of transferred layers are assessed, and the first PECVD epitaxial silicon solar cells transferred on glass are characterized. Copyright © 2016 John Wiley & Sons, Ltd.     

A Composite of Carbon‐Wrapped Mo2C Nanoparticle and Carbon Nanotube Formed Directly on Ni Foam as a High‐Performance Binder‐Free Cathode for Li‐O2 Batteries

Cathode design is indispensable for building Li‐O₂ batteries with long cycle life. A composite of carbon‐wrapped Mo₂C nanoparticles and carbon nanotubes is prepared on Ni foam by direct hydrolysis and carbonization of a gel composed of ammonium heptamolybdate tetrahydrate and hydroquinone resin. The Mo₂C nanoparticles with well‐controlled particle size act as a highly active oxygen reduction reactions/oxygen evolution reactions (ORR/OER) catalyst. The carbon coating can prevent the aggregation of the Mo₂C nanoparticles. The even distribution of Mo₂C nanoparticles results in the homogenous formation of discharge products. The skeleton of porous carbon with carbon nanotubes protrudes from the composite, resulting in extra voids when applied as a cathode for Li‐O₂ batteries. The batteries deliver a high discharge capacity of ≈10 400 mAh g^?1 and a low average charge voltage of ≈4.0 V at 200 mA g^?1. With a cutoff capacity of 1000 mAh g^?1, the Li‐O₂ batteries exhibit excellent charge–discharge cycling stability for over 300 cycles. The average potential polarization of discharge/charge gaps is only ≈0.9 V, demonstrating the high ORR and OER activities of these Mo₂C nanoparticles. The excellent cycling stability and low potential polarization provide new insights into the design of highly reversible and efficient cathode materials for Li‐O₂ batteries.     

Trimetallic Mn‐Fe‐Ni Oxide Nanoparticles Supported on Multi‐Walled Carbon Nanotubes as High‐Performance Bifunctional ORR/OER Electrocatalyst in Alkaline Media

Discovering precious metal‐free electrocatalysts exhibiting high activity and stability toward both the oxygen reduction (ORR) and the oxygen evolution (OER) reactions remains one of the main challenges for the development of reversible oxygen electrodes in rechargeable metal–air batteries and reversible electrolyzer/fuel cell systems. Herein, a highly active OER catalyst, Fe_0.3Ni_0.7O_X supported on oxygen‐functionalized multi‐walled carbon nanotubes, is substantially activated into a bifunctional ORR/OER catalyst by means of additional incorporation of MnO_X. The carbon nanotube‐supported trimetallic (Mn‐Ni‐Fe) oxide catalyst achieves remarkably low ORR and OER overpotentials with a low reversible ORR/OER overvoltage of only 0.73 V, as well as selective reduction of O₂ predominantly to OH^?. It is shown by means of rotating disk electrode and rotating ring disk electrode voltammetry that the combination of earth‐abundant transition metal oxides leads to strong synergistic interactions modulating catalytic activity. The applicability of the prepared catalyst for reversible ORR/OER electrocatalysis is evaluated by means of a four‐electrode configuration cell assembly comprising an integrated two‐layer bifunctional ORR/OER electrode system with the individual layers dedicated for the ORR and the OER to prevent deactivation of the ORR activity as commonly observed in single‐layer bifunctional ORR/OER electrodes after OER polarization.