Influence of Pt and Au nanophases on electrochromism of WO3 in nanostructure thin-film electrodes

We report electrochromic properties of WO₃ in Au–WO₃ and Pt–WO₃ nanostructure thin-film electrodes prepared by co-sputtering deposition method. The nanostructure electrodes consisted of Au or Pt metallic nanophase and a tungsten oxidative phase, indicating the formation of crystalline metallic nanophases in the amorphous oxide matrix. In particular, due to metallic nanophases, the modified electrochromic properties of WO₃ were observed in the Au–WO₃ and Pt–WO₃. The nanostructure electrodes showed a reverse optical modulation with respect to applied potentials in H₂SO₄ solution compared to that of pure WO₃ electrode. However, due to an excellent electrocatalytic activity of platinum for methanol electrooxidation at 25 °C, the electrochromism of the Pt–WO₃ in contrast with that of the Au–WO₃ was affected by the potentials for methanol electrooxidation in 2 M CH₃OH and 0.5 M H₂SO₄.     

Comments on stabilizing layered manganese oxide electrodes for Li batteries

An electrochemical study of structurally-integrated xLi₂MnO₃•(1 −x)LiMn_0.5Ni_0.5O₂ ‘composite’ materials has been undertaken to investigate the stability of electrochemically-activated electrodes at the Li₂MnO₃-rich end of the Li₂MnO₃–LiMn_0.5Ni_0.5O₂ tie-line, i.e., for 0.7 ≤ x ≤ 0.95. Excellent performance was observed for x = 0.7 in lithium half-cells; comparable to activated electrodes that have significantly lower values of x and are traditionally the preferred materials of choice. Electrodes with higher manganese content (x ≥ 0.8) showed significantly reduced performance. Implications for stabilizing low-cost, manganese-rich, layered lithium-metal-oxide electrode materials are discussed.     

Enhanced electrolytic generation of oxygen gas at binary nickel oxide–cobalt oxide nanoparticle-modified electrodes

This study addresses the enhancement of the oxygen evolution reaction (OER) on glassy carbon, Au, and Pt electrodes modified with binary catalysts composed of nickel oxide nanoparticles (nano-NiO_x) and cobalt oxide nanoparticles (nano-CoO_x). Binary NiO_x/CoO_x-modified electrodes (with NiO_x initially deposited) show a high catalytic activity and a marked stability which far exceeds that obtained at the individual oxide-modified electrodes. This enhancement is demonstrated by a marked negative shift (more than ca. 600 mV) in the onset potential of the OER compared to that obtained at the unmodified electrodes. The modified electrodes show a significantly higher long-term stability, over a period of 5 h of continuous electrolysis, without any significant loss of activity towards the OER in alkaline medium. The influence of the solution pH, the loading level, and sequence of deposition of each oxide on the electrocatalytic activity of the modified electrodes is addressed with an aim to maximize the catalytic activity of the modified electrodes towards the OER. SEM imaging is used to disclose the size and morphology of the fabricated nano-NiO_x and nano-CoO_x binary catalysts at the electrode surface.     

Novel concept of pseudocapacitor using stabilized lithium metal powder and non-lithiated metal oxide electrodes in organic electrolyte

A concept of using two non-prelithiated metal oxides (e.g., MnO₂, V₂O₅, and FeO_x) in both positive and negative electrodes in organic Li-ion electrolytes has been proposed and tested to improve the energy density of pseudocapacitors. To take the advantages of this concept, additional lithium source is essential to provide lithium ions during the charge–discharge cycles. The stabilized lithium metal powder (SLMP^?) developed by FMC Corp., provides such an essential Li⁺ source. Here we report the first result of the symmetric pseudocapacitor using two non-prelithiated metal oxide (i.e., manganese oxide/carbon nanotube (MnO₂/CNT)) electrodes, with added SLMP in one of them. The capacitor using the SLMP added MnO₂/CNT (positive) and pure MnO₂/CNT (negative) electrode in 1.2 M LiPF₆-EC:EMC electrolyte shows supercapacitive behaviors in 3.0 V voltage range. The addition of SLMP opens new opportunities of using the non-lithiated metal oxide electrodes in pseudocapacitors and hybrid electrochemical capacitors (ECs), which has not been possible before.     

Role of rhodium doping into lanthanum cobalt oxide (LaCoO3) perovskite and the induced bifunctional activity of oxygen evolution and reduction reactions in alkaline medium

Transition metal oxides, especially perovskites, have been considered effective electrocatalysts for the oxygen evolution (OER) and oxygen reduction (ORR) reactions in an alkaline solution. Here, a series of lanthanum cobalt rhodium oxide perovskites with the chemical formula LaCo_1-xRh_xO₃ (LCRO, 0.1 ≤ x ≤ 0.70) were prepared through the approach of solid-phase synthesis and their bifunctional electrocatalytic activity was assessed for both the OER and ORR. The crystallinity, morphology, surface, and electrocatalytic features of the LCRO were significantly correlated with the rhodium content. The LaCo_0.7Rh_0.3O₃ electrocatalysts with x = 0.3 showed enhanced electrocatalytic bifunctional performance with a substantially lower OER/ORR onset potential of 1.38/0.73 V vs HRE, smaller Tafel slope (116/90 mV/dec), and low charge-transfer resistance, which is the most efficient catalyst among the other studied ratios and superior to the pristine lanthanum cobalt oxide benchmark electrocatalysts. The LaCo_0.7Rh_0.3O₃ electrode exhibit good bifunctional electrocatalytic behavior and long-term durability with an OER and ORR onset potential gap (ΔE = E_OER ? E_ORR) of only 0.65 V, which could be credited to the enriched oxygen vacancies, lattice expansion and the improved electrical conductivity upon the doping of larger size of Rh ions. The LaCo_1-xRh_xO₃ catalysts are obtained from abundant materials that have the potential of highly-active bifunctional OER and ORR electrocatalysts.     

Unique CO-tolerance of Pt–WOx materials

Well-defined tungsten-oxide-supported platinum nanoparticles (Pt/WO_x) were elaborated by impregnation-reduction of a platinum salt onto commercial monoclinic WO₃. Field-emission gun scanning electron microscopy (FEG-SEM) and transmission electron microscopy (TEM) revealed that the Pt particles are well-distributed on the oxide support, present a narrow particle size distribution centered on ca. 2–3 nm and a low degree of agglomeration. Carbon black was added to ensure electronic percolation in the electrodes during the electrochemical measurements. CO_ads electrooxidation currents were monitored at potentials as low as 0.1 V vs. RHE on Pt/WO_x, demonstrating high CO-tolerance compared to carbon-supported Pt or PtRu catalysts.     

Conversion of porous PbO2 layers through galvanic displacement reaction with Mn2 + ions

The galvanic exchange between Mn^2 + ions and electrodeposited porous PbO₂ was studied to produce a porous oxide whose lower conductivity prevented its direct oxygen bubble-templated anodic deposition. Immersion of PbO₂ layers in acid acetate solutions of Mn^2 + led to the formation of amorphous MnO_x shell onto PbO₂. Due to its amorphous nature, MnO_x could not be proved to be MnO₂ by XRD. However, MnO_x was cathodically stripped at the same potential as MnO₂. The deposition of the MnO_x shell onto PbO₂ enhanced the capacity of the porous electrodes.     

Hydrogen generation from catalytic glucose oxidation by Fe-based electrocatalysts

Iron phosphide films (Fe₂P) grown in situ on stainless steel mesh (SSM) exhibit excellent electrocatalytic performance toward the glucose oxidation reaction (GOR) with robust durability. During GOR, the Fe₂P could be further transformed into the oxidized Fe species with high catalytic activity. The integrated two-electrode glucose electrolytic cell utilizing Fe₂P/SSM and Pt/C exhibited a cell voltage 300 mV lower than water splitting alone, indicating an efficient pathway for H₂ production. These features suggest that the replacement of the sluggish oxygen evolution reaction (OER) with the thermodynamically more favourable GOR in the Pt/C ||Fe₂P/SSM configuration is an attractive alternative for electrolytic H₂ generation.     

Structural and magnetic properties of orthorhombic LixMnO2

Rietveld refinement of the crystal and magnetic structures of Li_xMnO₂ (x = 0.98, 1.00, 1.02) are performed using neutron and X-ray measurements. A significant structural disorder due to the presence of manganese ions in lithium positions (Mn_Li) and lithium ions in manganese ones (Li_Mn) is found to be a common feature of Li_0.98MnO₂, Li_1.00MnO₂, and Li_1.02MnO₂.An essential anisotropy of the thermal-expansion coefficients of the lithium manganese oxides is observed in the temperature range of 1.5–300 K. Furthermore, the distortion of the oxygen octahedral environment around the manganese ions decreases when the temperature lowers. This is attributed to the strong exchange interactions between parallel exchange-coupled Mn chains. First-principles calculations of the effective exchange-interaction parameters in Li₁₆Mn₁₆O₃₂ confirm the essential antiferromagnetic interactions between the chains. In addition, a hypothetical (Li₁₅Mn)Mn₁₆O₃₂ structure where a lithium atom located between the Mn double layers is replaced by a manganese atom is considered. The calculations reveal that the presence of such defects results in appearance of a ferromagnetic component that agrees with the magnetic measurements.     

Comparative study of different types of graphenes as electrocatalysts for ascorbic acid

A comparative study regarding the electrocatalytic activity of graphene oxide (GO), chemically-reduced graphene oxide (crGO) and graphene produced by direct liquid exfoliation (dG) is presented. Sensors were developed by modifying glassy carbon (GC) electrodes with GO, crGO and dG and ascorbic acid was used as a pilot analyte. GC/GO electrodes offer substantially lower oxidation overpotential, up to 350 mV, compared with GC/crGO, GC/dG and unmodified GC electrodes. In addition, the different carbon-to-oxygen atomic ratios in GO, as it occurs depending on the synthetic route, were found to have a remarkable effect on the performance of the sensors. Reduction of GO was achieved by immersing the modified electrodes into a stirred solution of NaBH₄ for 10 min at room temperature. This process was used alternatively of the time consuming and laborious process of hydrazine, and its effectiveness was confirmed by cyclic voltammetry and electrochemical impedance spectroscopy. Analytical utility of the sensors is demonstrated.     

Amperometric biosensors based on deposition of gold and platinum nanoparticles on polyvinylferrocene modified electrode for xanthine detection

In this study, new xanthine biosensors, XO/Au/PVF/Pt and XO/Pt/PVF/Pt, based on electroless deposition of gold(Au) and platinum(Pt) nanoparticles on polyvinylferrocene(PVF) coated Pt electrode for detection of xanthine were presented. The amperometric responses of the enzyme electrodes were measured at the constant potential, which was due to the electrooxidation of enzymatically produced H₂O₂. Compared with XO/PVF/Pt electrode, XO/Au/PVF/Pt and XO/Pt/PVF/Pt exhibited excellent electrocatalytic activity towards the oxidation of the analyte. Effect of Au and Pt nanoparticles was investigated by monitoring the response currents at the different deposition times and the different concentrations of KAuCl₄ and PtBr₂. Under the optimal conditions, the calibration curves of XO/Au/PVF/Pt and XO/Pt/PVF/Pt were obtained over the range of 2.5 × 10^?3 to 0.56 mM and 2.0 × 10^?3 to 0.66 mM, respectively. The detection limits were 7.5 × 10^?4 mM for XO/Au/PVF/Pt and 6.0 × 10^?4 mM for XO/Pt/PVF/Pt. The effects of interferents, the operational and the storage stabilities of the biosensors and the applicabilities of the proposed biosensors to the drug samples analysis were also evaluated.     

3-D composite electrodes for high performance PEM fuel cells composed of Pt supported on nitrogen-doped carbon nanotubes grown on carbon paper

The 3-D composite electrodes consisting of Pt nanoparticles supported on nitrogen-doped carbon nanotubes (CN_x) grown directly on carbon paper were successfully prepared. The effect of the nitrogen atom incorporation in carbon nanotubes (CNTs) on the Pt nanoparticle dispersion and catalytic activities for the oxygen reduction reaction has been investigated. Compared to regular CNTs, highly dispersed Pt nanoparticles with smaller size (2–3 nm) and higher electrochemical Pt surface area as well as higher fuel cell performance were obtained for CN_x.     

Choline biosensors based on a bi-electrocatalytic property of MnO2 nanoparticles modified electrodes to H2O2

An interesting mode of reactivity of MnO₂ nanoparticles modified electrode in the presence of H₂O₂ is reported. The MnO₂ nanoparticles modified electrodes show a bi-direction electrocatalytic ability toward the reduction/oxidation of H₂O₂. Based on this property, a choline biosensor was fabricated via a direct and facile electrochemical deposition of a biocomposite that was made of chitosan hydrogel, choline oxidase (ChOx) and MnO₂ nanoparticles onto a glassy carbon (GC) electrode. The biocomposite is homogeneous and easily prepared and provides a shelter for the enzyme to retain its bioactivity. The results of square wave voltammetry showed that the electrocatalytic reduction currents increased linearly with the increase of choline chloride concentration in the range of 1.0 × 10⁻⁵ –2.1 × 10⁻³ M and no obvious interference from ascorbic acid and uric acid was observed. Good reproducibility and stability were obtained. A possible reaction mechanism was proposed.     

Anomalous capacity and cycling stability of xLi2MnO3 · (1 − x)LiMO2 electrodes (M = Mn,Ni, Co) in lithium batteries at 50 °C

Transition metal oxides with composite xLi₂MnO₃ ·  (1 − x)LiMO₂ rocksalt structures (M = Mn, Ni, Co) are of interest as a new generation of cathode materials for high energy density lithium-ion batteries. After electrochemical activation to 4.6 or 4.8 V (vs. Li⁰) at 50 °C, xLi₂MnO₃ · (1 − x)LiMn_0.33Ni_0.33Co_0.33O₂ (x = 0.5, 0.7) electrodes deliver initial discharge capacities (>300 mAh/g) at a low current rate (0.05 mA/cm²) that exceed the theoretical values for lithiation back to the rocksalt stoichiometry (240–260 mAh/g), at least during the early charge/discharge cycles of the cells. Attention is drawn to previous reports of similar, but unaccounted and unexplained anomalous behavior of these types of electrode materials. Possible reasons for this anomalous capacity are suggested. Indications are that electrodes in which M = Mn, Ni and Co do not cycle with the same stability at 50 °C as those without cobalt.     

Lithium–manganese–nickel-oxide electrodes with integrated layered–spinel structures for lithium batteries

A series of lithium–manganese–nickel-oxide compositions that can be represented in three-component notation, xLi[Mn_1.5Ni_0.5]O₄ · (1 − x){Li₂MnO₃ · Li(Mn_0.5Ni_0.5)O₂}, in which a spinel component, Li[Mn_1.5Ni_0.5]O₄, and two layered components, Li₂MnO₃ and Li(Mn_0.5Ni_0.5)O₂, are structurally integrated in a highly complex manner, have been evaluated as electrodes in lithium cells for x = 1, 0.75, 0.50, 0.25 and 0. In this series of compounds, which is defined by the Li[Mn_1.5Ni_0.5]O₄–{Li₂MnO₃ · Li(Mn_0.5Ni_0.5)O₂} tie-line in the Li[Mn_1.5Ni_0.5]O₄–Li₂MnO₃–Li(Mn_0.5Ni_0.5)O₂ phase diagram, the Mn:Ni ratio in the spinel and the combined layered Li₂MnO₃ · Li(Mn_0.5Ni_0.5)O₂ components is always 3:1. Powder X-ray diffraction patterns of the end members and the electrochemical profiles of cells with these electrodes are consistent with those expected for the spinel Li[Mn_1.5Ni_0.5]O₄ (x = 1) and for ‘composite’ Li₂MnO₃ · Li(Mn_0.5Ni_0.5)O₂ layered electrode structures (x = 0). Electrodes with intermediate values of x exhibit both spinel and layered character and yield extremely high capacities, reaching more than 250 mA h/g with good cycling stability between 2.0 V and 4.95 V vs. Li° at a current rate of 0.1 mA/cm².     

Au-coated carbon cathodes for improved oxygen reduction and evolution kinetics in aprotic Li–O2 batteries

Metal-oxygen systems are an attractive option to enhance the specific energy of secondary batteries. However, their power is limited by the oxygen electrode. In this communication we address the issue of the sluggish kinetics of the oxygen cathode in the aprotic Li–O₂ batteries. The electrochemical performances of newly designed carbon electrodes coated with 50 Å thick Au layer are evaluated and compared with those of unmodified electrodes. Despite the low noble metal content (~ 2 wt.%), the Li–O₂ batteries built with the abovementioned Au-coated cathodes show considerably enhanced kinetics as demonstrated by the higher onset potentials for the oxygen reduction reaction (~ 2.6 V at a current rate of 1000 mA g^− 1), together with reduced oxygen evolution potentials.     

A Molecular Approach to Manganese Nitride Acting as a High Performance Electrocatalyst in the Oxygen Evolution Reaction

The scalable synthesis of phase‐pure crystalline manganese nitride (Mn₃N₂) from a molecular precursor is reported. It acts as a superiorly active and durable electrocatalyst in the oxygen evolution reaction (OER) from water under alkaline conditions. While electrophoretically deposited Mn₃N₂ on fluorine tin oxide (FTO) requires an overpotential of 390 mV, the latter is substantially decreased to merely 270 mV on nickel foam (NF) at a current density of 10 mA cm^?2 with a durability of weeks. The high performance of this material is due to the rapid transformation of manganese sites at the surface of Mn₃N₂ into an amorphous active MnO_x overlayer under operation conditions intimately connected with metallic Mn₃N₂, which increases the charge transfer from the active catalyst surface to the electrode substrates and thus outperforms the electrocatalytic activity in comparison to solely MnO_x‐based OER catalysts.     

Quasi-reversible two-electron reduction of oxygen at gold electrodes modified with a self-assembled submonolayer of cysteine

The electrochemical reduction of molecular oxygen (O₂) has been performed at gold electrodes modified with a submonolayer of a self-assembly (sub-SAM/Au) of a thiol compound (typically cysteine (CYST)) in O₂-saturated 0.5 M KOH. At bare gold electrode O₂ reduction reaction proceeds irreversibly, while this reaction is totally hindered at gold electrodes with a compact structure of CYST over its surface. The partial reductive desorption of the compact CYST monolayer was achieved by controlling the potential of the CYST/Au electrode, leading to the formation of a submonolayer coverage of the thiol compound over the Au electrode surface (sub-SAM/Au), at which the CYST molecules selectively block the Au(1 0 0) and Au(1 1 0) fractions (the so-called rough domains) of the polycrystalline Au while the Au(1 1 1) component (the so-called smooth domains) remains bare (i.e., uncovered with CYST). This sub-SAM/Au electrode extraordinarily exhibits a quasi-reversible two-electron reduction of molecular oxygen (O₂) in alkaline medium with a peak separation (ΔE_p) between the cathodic and anodic peak potentials (E_p^c,E_p^a) of about 60 mV. The ratio of the anodic current to the cathodic one is close to unity. The formal potential (E^o′) of this reaction is found to equal −150 mV vs. Ag/AgCl/KCl(sat.).     

FeAgMo2O8 — A novel oxygen evolution catalyst material for alkaline metal–air batteries

This paper reports about FeAgMo₂O₈ — a novel oxygen evolution catalyst material for secondary (rechargeable) metal–air batteries. Bifunctional air electrodes were made using FeAgMo₂O₈ as a charging catalyst for oxygen evolution reaction (OER) and silverized carbon black (Ag/C) was employed as a discharging catalyst for oxygen reduction reaction (ORR). Corresponding air electrodes were investigated using 10 M KOH as an electrolyte. At current densities between 20 and 50 mA per cm² we observed discharging and charging voltages of 1.20 to 1.15 V and 1.96 to 2.05 V, respectively.     

Enhancing the rate capability of high capacity xLi2MnO3 · (1 − x)LiMO2 (M = Mn,Ni, Co) electrodes by Li–Ni–PO4 treatment

The rate capability of high capacity xLi₂MnO₃ · (1 ? x)LiMO₂ (M = Mn, Ni, Co) electrodes for lithium-ion batteries has been significantly enhanced by stabilizing the electrode surface by reaction with a Li–Ni–PO₄ solution, followed by a heat-treatment step. Reversible capacities of 250 mAh/g at a C/11 rate, 225 mAh/g at C/2 and 200 mAh/g at C/1 have been obtained from 0.5Li₂MnO₃ · 0.5LiNi_0.44Co_0.25Mn_0.31O₂ electrodes between 4.6 and 2.0 V. The data bode well for their implementation in batteries that meet the 40-mile range requirement for plug-in hybrid vehicles.