A glassy carbon electrode modified with a film composed of cobalt oxide nanoparticles and graphene for electrochemical sensing of H2O2

We have prepared a graphene-based hybrid nanomaterial by electrochemical deposition of cobalt oxide nanoparticles (CoO_xNPs) on the surface of electrochemically reduced graphene oxide deposited on a glassy carbon electrode (GCE). Scanning electron microscopy and cyclic voltammetry were used to characterize the immobilized nanoparticles. Electrochemical determination of H₂O₂ is demonstrated with the modified GCE at pH 7. Compared to GCEs modified with CoO_xNPs or graphene sheets only, the new electrode displays larger oxidative current response to H₂O₂, probably due to the synergistic effects between the graphene sheets and the CoO_xNPs. The sensor responds to H₂O₂ with a sensitivity of 148.6 μA mM^?1 cm^?2 and a linear response range from 5 μM to 1 mM. The detection limit is 0.2 μM at a signal to noise ratio (SNR) of three. The method was successfully applied to the determination of H₂O₂ in hydrogen peroxide samples.

Chemoselective hydrogenation of phenol to cyclohexanol using heterogenized cobalt oxide catalysts

Cobalt oxide nanoparticles (NPs) supported on porous carbon (CoO_x@CN) were fabricated by one-pot method and the hybrids could efficiently and selectively hydrogenate phenol to cyclohexanol with a high yield of 98%.     

Photodegradation of 2-nitrophenol catalyzed by CoO, CoS and CoO/CoS nanoparticles

The nanoparticles of CoO, CoS and CoO/CoS composite are synthesized using precipitation method. The X-ray diffraction, UV–Vis absorption spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy and FT-IR spectroscopy are used to characterize the prepared nanoparticles. The EDX analysis shows the formation of CoO_0.67S_0.33 composite. The XRD pattern indicates the hexagonal structure for nanocomposite. The formation of Co–O and Co–S bonds is confirmed by FT-IR spectra. The band-gap energies of 2.97, 3.06 and 2.91 eV are obtained from UV–Vis spectra of CoO, CoS and CoO/CoS nanoparticles, respectively. The results of photodegradation of 2-nitrophenol show that the photoreactivity order of nanocatalysts is CoO/CoS > CoO > CoS. The pseudo first-order kinetic rate constants of 6.4 × 10^?3, 4.3 × 10^?3 and 12.2 × 10^?3 min^?1 are obtained for CoO, CoS and CoO/CoS nanoparticles, respectively, at photodegradation reaction conditions of pH 10, 30 mg/L of 2-NP and 1.3 g/L of the catalyst. The proposed nanocomposite shows an acceptable reusability and stability against photocorrosion in four-cycle photodegradation experiments.     

Electrochemical Fabrication of Cobalt Oxides/Nanoporous Gold Composite Electrode and its Nonenzymatic Glucose Sensing Performance

A nonenzymatic glucose sensor was successfully established by electrochemically decorating cobalt oxides (CoO_x) on a nanoporous gold electrode (NPG) using cobalt hexacyanoferrate (CoHCF) as a precursor. It exhibited high sensitivity and long‐term stability as well as satisfactory quantification of glucose concentration in human serum samples. The morphology and surface analysis of the resulting CoO_x/NPG were carefully characterized. Two detection methods, cyclic voltammetry and amperometry, were employed to evaluate the performance of CoO_x/NPG towards glucose sensing in alkaline solution. Using cyclic voltammetry, at ?0.5 V, the glucose partial oxidation peak current is linear to the glucose concentration up to 14 mM with a sensitivity of 283.7 µA mM^?1 cm^?2. A linear amperometric response at 0.55 V was obtained in the glucose concentration range from 2 µM to 2 mM with a sensitivity of 2025 µA mM^?1 cm^?2 and a response time <3 s.     

Synthesis and electrochemical evaluation of La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> catalysts for zinc-air batteries

La_1-x Sr _x MnO₃ (x?=?0.1～0.4) catalysts for primary and rechargeable zinc-air batteries have been successfully synthesized by the citrate method and their electrochemical properties measured. The materials can catalyze both ORR and OER, and the one with ideal composition of La_0.8Sr_0.2MnO₃ catalyst exhibits the highest catalytic activity and durability in alkaline medium. The resulting primary zinc-air cell shows a peak power density of 146 mW cm^?2 at 235 mA cm^?2. The secondary cell exhibits a charge-discharge voltage gap of 1.0 V at 10 mA cm^?2, which is highly stable over many charge-discharge cycles.     

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.     

Effect of surfactant on the morphology and capacitive performance of porous NiCo2O4

A promising nickel cobaltite oxide (NiCo₂O₄) composite electrode material was successfully synthesized by a sol-gel method and followed by a simple sintering process. The microstructure and surface morphology of NiCo₂O₄ modified by hexadecyltrimethylammonium bromide (CTAB) and polyvinyl alcohol were physically characterized by powder X-ray diffraction and scanning electron microscopy. Meanwhile, electrochemical performance was widely investigated in 2 M KOH aqueous electrolyte using cyclic voltammetry, galvanostatic charge-discharge test, and electrochemical impedance spectroscopy. The results show that evident porous microstructure was successfully fabricated by CTAB. The NiCo₂O₄ controlled by CTAB exhibited highly specific capacitance of 1,440 F?g^?1 at a current density of 5 mA?cm^?2. Remarkably, it still displays desirable cycle retention of 94.1 % over 1,000 cycle numbers at a current density of 20 mA?cm^?2. The excellent electrochemical performance suggests its potential application in electrode material for electrochemical capacitors.     

Crystal Structure, Electric and Magnetic Properties of Layered Cobaltite β-NaxCoO2

The layered oxide thermoelectric material β-Na_0.67CoO₂ has been studied by powder neutron diffraction, electric and magnetic measurements. This compound includes an edge-sharing CoO₆ slab and a highly vacant Na⁺ sheet in a unit cell (space group symmetry C2/m, a=4.9023(4) Å, b=2.8280(2) Å, c=5.7198(6) Å and β=105.964(6)° at 300 K). The evaluated formal valence of cobalt ion, +3.33(1), is ascribed to the coexistence of Co³⁺ and Co⁴⁺ in the ratio 2:1. Polycrystalline β-Na_0.67CoO₂, a p-type thermoelectric material, exhibits metallic behavior of the electric resistivity below 300 K. The Curie-Weiss-type magnetic susceptibility indicates antiferromagnetic interactions between magnetic cobalt ions in the edge-sharing CoO₆ slab.     

Preparation and thermal stability of trioxalatocobaltates of bivalent metals KM2+ [Co(C2O4)3]·xH2O

Trioxalatocobaltates of bivalent metals KM²⁺[Co(C₂O₄)₃]·x H₂O, with M²⁺ = Ba, Sr, Ca and Pb, have been prepared, characterized and their thermal behaviour studied. The compounds decompose to yield potassium carbonate, bivalent metal carbonate or oxide and cobalt oxide as final products. The formation of the final products of decomposition is influenced by the surrounding atmosphere. Bivalent metal cobaltites of the types KM²⁺CoO₃ and M²⁺CoO_3—x are not identified among the final products of decomposition. The study brings out the importance of the decomposition mode of the precursor in producing the desired end products.     

The preparation of LaSr<Subscript>3</Subscript>Fe<Subscript>3</Subscript>O<Subscript>10 − <Emphasis Type="Italic">δ</Emphasis></Subscript> and its electrochemical performance

LaSr₃Fe₃O_10 ? δ powders were synthesized by hydrothermal method and characterized by XRD and SEM. The XRD patterns showed that the sample calcined at 1000 °C was single phase and the sample calcined at 900 °C had tiny amount of LaSrFeO₄ phase. The single-phase LaSr₃Fe₃O_10 ? δ powders were used to prepare test electrode. The capacitive behaviors of LaSr₃Fe₃O_10 ? δ electrode were analyzed by cyclic voltammetry, galvanostatic charge-discharge techniques, and electrochemical impedance spectroscopy. The electrochemical results showed a capacity as high as 470 F g^?1 at a scan rate of 1 mV s^?1 and 380 F g^?1 at a charge-discharge current density of 0.1 A g^?1 in 6 M KOH solution. The electrode showed good cyclic stability since its capacitive retention is 87.1% after 1000 charge-discharge cycles. The electrochemical performances suggest that LaSr₃Fe₃O_10 ? δ could be a potential candidate as a capacitive electrode material.     

Behavior of Co4+ ion in K2NiF4-type (Ca1+xSm1−x)CoO4

Orthorhombic K₂NiF₄-type (Ca_1+xSm_1−x)CoO₄ (0.00 ≤ x ≤0.15) with space group Bmab has been synthesized by the polymerized complex route. The cell parameters (a and b) decrease, while the cell parameter (c) increases with increasing Co⁴⁺ ion content. The global instability index (GII) indicates that the crystal stability of (Ca_1+xSm_1−x)CoO₄ is not influenced by the Co⁴⁺ ion content. (Ca_1+xSm_1−x)CoO₄ is a p-type semiconductor and exhibits hopping conductivity in the small-polaron model at low temperatures. The magnetic measurement indicates that (Ca_1+xSm_1−x)CoO₄ shows paramagnetic behavior above 5 K, and that the spin state of both the Co³⁺ and Co⁴⁺ ions is low. The Co⁴⁺ ion acts as an acceptor, and the electron transfer becomes active through the Co³⁺–O–Co⁴⁺ path as the Co⁴⁺ ions increase.     

Les bronzes de cobalt KxCoO2 (x < 1). L'oxyde KCoO2

The reaction between potassium and cobalt oxides leads to two bronze-type phases with formula K_xCoO₂ (x = 0.50 and x = 0.67), and to a KCoO₂ oxide with two allotropic forms. The lattice of K_xCoO₂ is built up by sheets of (CoO₂)_n octahedra between which potassium ions are inserted with a prismatic coordination; they have a metallic behavior. The structures of both KCoO₂ varieties are related to the cristobalite type. The oxidation state of cobalt is discussed on the basis of structural, optical, and magnetical data.     

Ultrahigh‐Content Nitrogen‐doped Carbon Encapsulating Cobalt NPs as Catalyst for Oxidative Esterification of Furfural

It is an attractive and challenging topic to endow non‐noble metal catalysts with high efficiency via a nitrogen‐doping approach. In this study, a nitrogen‐doped carbon catalyst with high nitrogen content encapsulating cobalt NPs (CoO_x@N‐C(g)) was synthesized, and characterized in detail by XRD, HRTEM, N₂‐physisorption, ICP, CO₂‐TPD, and XPS techniques. g‐C₃N₄ nanosheets act as nitrogen source and self‐sacrificing templates, giving rise to an ultrahigh nitrogen content of 14.0 %, much higher than those using bulk g‐C₃N₄ (4.4 %) via the same synthesis procedures. As a result, CoO_x@N‐C(g) exhibited the highest performance in the oxidative esterification of biomass‐derived platform furfural to methylfuroate under base‐free conditions, achieving 95.0 % conversion and 97.1 % selectivity toward methylfuroate under 0.5 MPa O₂ at 100 °C for 6 h, far exceeding those of other cobalt‐based catalysts. The high efficiency of CoO_x@N‐C(g) was closely related to its high ratio of pyridinic nitrogen species that may act as Lewis basic sites as well as its capacity for the activation of dioxygen to superoxide radical O₂^.?.     

Enhanced visible-light photocatalytic activities of porous olive-shaped sulfur-doped BiVO4-supported cobalt oxides

Porous S-doped bismuth vanadate with an olive-like morphology and its supported cobalt oxide (y wt% CoO_x/BiVO_4−δS_0.08, y = 0.1, 0.8, and 1.6) photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt% CoO_x/BiVO_4−δS_0.08 photocatalysts were single-phase with a monoclinic scheetlite structure, a porous olive-like morphology, a surface area of 8.8–9.2 m²/g, and a bandgap energy of 2.38–2.41 eV. There was the co-presence of surface Bi⁵⁺, Bi³⁺, V⁵⁺, V³⁺, Co³⁺, and Co²⁺ species in y wt% CoO_x/BiVO_4−δS_0.08. The 0.8 wt% CoO_x/BiVO_4−δS_0.08 sample performed the best for methylene blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and CoO_x co-doping, higher oxygen adspecies concentration, and lower bandgap energy were responsible for the excellent visible-light-driven catalytic activity of 0.8 wt% CoO_x/BiVO_4−δS_0.08.     

<Superscript>1</Superscript>H and <Superscript>7</Superscript>Li NMR in defect cobaltite Li<Subscript>0.6</Subscript>CoO<Subscript>2</Subscript>

Within a temperature range of 120–330 K, ⁷Li NMR spectra in Li_0.6CoO₂ are obtained. It is shown that as the temperature increases, both smooth and stepwise variation of ⁷Li NMR contact shifts occurs. The observed effects are explained by the occupation of the excited levels of cobalt ions. The stepwise change of the resonance line width depending on the temperature is revealed. It is driven by the features of the diffusive motion of lithium ions. The calculation of the ¹H NMR line shape provides the determination of the ratio of one-, two-, and three-spin proton clusters in Li_0.6CoO₂·xH₂O.     

Structural and thermal characterization of Zn2−xCoxTiO4

In this work, spinels with the general formula Zn_2?xCo_xTiO₄ were synthesized by the polymeric precursor method and thermally treated at 1,000 °C. The powder precursors were characterized by TG/DTA. A decrease in the DTA peak temperature with the amount of zinc was observed. After the thermal treatment, the characterizations were performed by XRD, IR, colorimetry and UV/VIS spectroscopy. The XRD patterns of all the samples showed the presence of the spinel phase. Infrared spectroscopy showed the presence of ester complexes for Zn₂TiO₄ after thermal treatment at 500 °C, which disappeared after cobalt addition, indicating that organic material elimination was favored.     

Charge compensation and oxidation in NaxCoO2−δ and LixCoO2−δ studied by XANES

A comparative study on the oxidation and charge compensation in the A_xCoO_2−δ systems, A=Na (x=0.75, 0.47, 0.36, 0.12) and Li (x=1, 0.49, 0.05), using X-ray absorption spectroscopy at O 1s and Co 2p edges is reported. Both the O 1s and Co 2p XANES results show that upon removal of alkali metal from A_xCoO_2−δ the valence of cobalt increases more in Li_xCoO_2−δ than in Na_xCoO_2−δ. In addition, the data of O 1s XANES indicate that charge compensation by oxygen is more pronounced in Na_xCoO_2−δ than in Li_xCoO_2−δ.     

Electron transport and magnetic properties of La1−xSrxCo1−yTiyO3 (x = 0a or x = yb)

The two systems (a) and (b) for different values of x were synthesized. Their electron transport and magnetic properties show a change in behavior above a critical value of x. Unlike the system La_1?xSr_xCoO₃, itinerant electron ferromagnetism is not observed. This is explained on the basis of the absence of an itinerant band of Co⁴⁺ whose generation is restricted on account of substitution of Ti⁴⁺. Electron transport in these two systems is compared with that of LaCoO₃ or La_1?xSr_xCoO₃ and is discussed in view of the presence of different valence states of cobalt and change in crystal field splitting. Spin-state equilibria in these two systems are similar to that in LaCoO₃.     

Preparation,spectroscopic and thermal analysis of hexa-hydrazine nickel cobalt ferrous succinate precursor and study of solid-state properties of its nanosized thermal product,Ni<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript>

Nickel cobalt ferrite, Ni_0.5Co_0.5Fe₂O₄, has been prepared by precursor combustion technique from hexa-hydrazine nickel cobalt ferrous succinate precursor. The precursor was characterized by chemical analysis, CHNS analysis, infrared spectroscopy, TG–DTA and mass loss studies. The thermal data show how the precursor decomposes in four steps to give stable ferrite phase. The precursor decomposes autocatalytically once initially ignited, to give the ‘as-prepared’ nano-spinel ferrite. The X-ray diffraction analysis reveals single cubic spinel phase structure. The infrared measurements between 4000 and 350 cm^?1 confirmed the intrinsic cation vibrations of the spinel structure. The SEM image clearly shows the nanosized nature of the ferrite. The dielectric constant and loss tangent are found to decrease with increase in frequency which is due to Maxwell–Wagner interfacial polarization. The loss tangent shows a relaxation peak at ~1 kHz. The variation of DC electrical resistivity with temperature indicates semiconductor behaviour. The temperature- and field-dependent magnetization data of ‘as-prepared’ ferrite reveal that the lattice has either a canted or partially misaligned spin structure due to the nanosized nature of the ferrite.     

Influence of Ca2+ substitution on thermal,structural, and conductivity behavior of Bi1−xCaxFeO3−y (0.40 ≤ x ≤ 0.55)

Bi_1?xCa_xFeO_3?y (0.40 ≤ x ≤ 0.55) perovskite oxides have been synthesized by solid-state reaction method to study their properties as a cathode material for intermediate temperature solid oxide fuel cells. The as prepared samples were characterized by X-ray diffraction, differential thermal analyzer/thermogravimetry, dilatometer, and impedance spectroscopy to study their structural, thermal, and electrical properties. The Rietveld refinement results confirmed that all the samples exhibit tetragonal structure with P4mm space group. In addition to this, sample x = 0.55 exhibits Ca₂Fe₂O₅ as a secondary phase. It has been observed that lattice parameters decrease with increase in calcium content. The thermal expansion coefficient and ionic conductivity increases with increase in calcium content up to x = 0.50. The highest ionic conductivity is observed for Bi_0.5Ca_0.5FeO_3?y i.e. 1.71 × 10^?2 S cm^?1.