Electroless oxidation of diamond surfaces in ceric and ferricyanide solutions: An easy way to produce “C-O” functional groups

Despite many works are devoted to oxidation of diamond surfaces, it is still a challenge, to successfully produce well defined “C-O” functions, particularly for functionalization purposes. In this paper we describe and compare, for the first time, the “electroless” oxidation of as-deposited polycrystalline boron-doped diamond (BDD) films in ceric and ferricyanide solutions at room temperature. Both reactions efficiently generate oxygen functionalities on BDD surface. While a higher amount of “C-O” moieties is produced with Ce⁴⁺ as oxidizing agent, the use of ferricyanide specie seems the most interesting to specifically generate hydroxyl groups. Additionally, this easy to perform oxidative method appears not damaging for diamond surfaces and adapted to conductive or non-conductive materials. The resulting surfaces were characterized using X-ray photoelectron spectroscopy, contact angle and capacitance-voltage analysis.     

Electrochemical incineration of chloranilic acid using Ti/IrO2, Pb/PbO2 and Si/BDD electrodes

The electrochemical oxidation of chloranilic acid (CAA) has been studied in acidic media at Pb/PbO₂, boron-doped diamond (Si/BDD) and Ti/IrO₂ electrodes by bulk electrolysis experiments under galvanostatic control. The obtained results have clearly shown that the electrode material is an important parameter for the optimization of such processes, deciding of their mechanism and of the oxidation products. It has been observed that the oxidation of CAA generates several intermediates eventually leading to its complete mineralization. Different current efficiencies were obtained at Pb/PbO₂ and BDD, depending on the applied current density in the range from 6.3 to 50 mA cm⁻². Also the effect of the temperature on Pb/PbO₂ and BDD electrodes was studied.UV spectrometric measurements were carried out at all anodic materials, with applied current density of 25 and 50 mA cm⁻². These results showed a faster CAA elimination at the BDD electrode. Finally, a mechanism for the electrochemical oxidation of CAA has been proposed according to the results obtained with the HPLC technique.     

Single-phased emission-tunable Ca3Si2O7:Ce,Eu phosphors for white light-emitting diodes

A series of single-phased emission-tunable Ca₃Si₂O₇:Ce³⁺, Eu²⁺ phosphors has been prepared by the solid-state reaction method. The phosphors show two intense emission bands at about 450 nm and 610 nm, which are attributed to the 5d→4f transitions of Ce³⁺ and Eu²⁺ ions, respectively. The emission colors of Ca₃Si₂O₇:Ce³⁺, Eu²⁺ phosphors vary from blue (0.148, 0.147) to white (0.309, 0.260), and eventually to orange (0.407, 0.319) by tuning the Eu²⁺/Ce³⁺ ratio. Energy transfer from Ce³⁺ to Eu²⁺ is studied by luminescence spectra and energy transfer efficiency. The results show an electric quadrupole–quadrupole interaction plays an important role in the process of energy transfer. The phosphors with tunable emission are suitable for application in white light-emitting diodes.     

Luminescent properties of a novel afterglow phosphor Sr3Al2O5Cl2:Eu,Ce

A series of Eu²⁺ and Ce³⁺ doped/co-doped Sr₃Al₂O₅Cl₂ afterglow phosphors that presented various bright colors were successfully synthesized via high temperature solid state reaction. The structure and luminescence properties of the obtained samples were characterized by X-ray powder diffraction (XRD), photoluminescence (PL) spectra and decay curves as well as the thermoluminescence (TL) glow curves. The XRD results showed that all the phase could be indexed to the orthorhombic structure with the space group P2₁2₁2₁. After being exposed to a 254 nm or 365 nm mercury lamp, blue/yellow-orange afterglow emissions with broad bands peaking around 620 nm/435 nm, which were ascribed to the characteristic 4f⁶5d–4f⁷/5d¹–4f¹ transitions of Eu²⁺/Ce³⁺, could be observed in phosphors of Sr₃Al₂O₅Cl₂:Eu²⁺/Sr₃Al₂O₅Cl₂:Ce³⁺, respectively. Because of the overlap spectral range between the Sr₃Al₂O₅Cl₂:Eu²⁺ and Sr₃Al₂O₅Cl₂:Ce³⁺ phosphors, the energy transfer (ET) from Ce³⁺ to Eu²⁺ occurred. The related ET process was discussed in detail. Moreover, the incorporation of Ce³⁺ could significantly prolong the afterglow duration of Sr₃Al₂O₅Cl₂:Eu²⁺ phosphor, which was due to the increase of trap concentration. Consequently, 6 h of the afterglow duration could be observed in Sr₃Al₂O₅Cl₂:1.0%Eu²⁺, 0.5%Ce³⁺ sample, exhibiting much longer than that of Sr₃Al₂O₅Cl₂: 1.0%Eu²⁺ (3 h). From the afterglow decay curves and the fitting results, the optimal concentration of Ce³⁺ for the enhanced afterglow property was experimentally determined to be 0.5%.     

The first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V

In this research, we studied the first cycle characteristics of Li[Ni_1/3Co_1/3Mn_1/3]O₂ charged up to 4.7 V. Properties, such as valence state of the transition metals and crystallographic features, were analyzed by X-ray absorption spectroscopy and X-ray and neutron diffractions. Especially, two plateaus observed around 3.75 and 4.54 V were investigated by ex situ X-ray absorption spectroscopy. XANES studies showed that the oxidation states of transition metals in Li[Ni_1/3Co_1/3Mn_1/3]O₂ are mostly Ni²⁺, Co³⁺ and Mn⁴⁺. Based on neutron diffraction Rietveld analysis, there is about 6% of all nickel divalent (Ni²⁺) ions mixed with lithium ions (cation mixing). Meanwhile, it was found that the oxidation reaction of Ni²⁺/Ni⁴⁺ is related to the lower plateau around 3.75 V, but that of Co³⁺/Co⁴⁺ seems to occur entire range of x in Li_1−x[Ni_1/3Co_1/3Mn_1/3]O₂. Small volume change during cycling was attributed to the opposite variation of lattice parameter “c” and “a” with charging-discharging.     

Nanostructured co-precipitated Ce0.9Ln0.1O2 (Ln = La,Pr, Sm,Nd, Gd,Tb, Dy,or Er) for thermochemical conversion of CO2

The influence of lanthanide metal cations doped into the CeO₂ crystal structure (to form Ce_0.9Ln_0.1O₂; Ln = La, Pr, Nd, Sm, Gd, Tb, Dy, or Er) on thermochemical reduction and the CO₂ splitting ability of Ce_0.9Ln_0.1O₂ is scrutinized using thermogravimetric analysis. Ce_0.9Ln_0.1O₂ redox materials are effectively synthesized by co-precipitation of hydroxides. As-synthesized Ce_0.9Ln_0.1O₂ redox materials are further characterized based on their phase composition, crystallite size, surface area, and morphology using powder X-ray diffraction, Brunauer-Emmett-Teller surface area analysis, and scanning electron microscopy. The thermal reduction and CO₂ splitting aptitude of Ce_0.9Ln_0.1O₂ redox materials are examined by performing 10 consecutive thermochemical cycles. The results imply that insertion of Sm³⁺, Er³⁺, Tb³⁺, Dy³⁺, and La⁺³ in place of Ce⁴⁺ in the fluorite crystal structure of CeO₂ (forming Ce_0.9Ln_0.1O₂) enhances the O₂ liberation by 22.5, 14.6, 12.6, 5.85, and 2.96 μmol O₂/g·cycle, respectively. Besides, CeLa is observed to be more active towards the CO₂ splitting reaction than CeO₂ and the other Ce_0.9Ln_0.1O₂ redox materials investigated in this study.     

Methane combustion over Pd/ZrO2/SiC,Pd/CeO2/SiC,and Pd/Zr0.5Ce0.5O2/SiC catalysts

The performances of different promoters (CeO₂, ZrO₂ and Ce_0.5Zr_0.5O₂ solid solution) modified Pd/SiC catalysts for methane combustion are studied. XRD and XPS results showed that Zr⁴⁺ could be incorporated into the CeO₂ lattice to form Zr_0.5Ce_0.5O₂ solid solution. The catalytic activities of Pd/CeO₂/SiC and Pd/ZrO₂/SiC are lower than that of Pd/Zr_0.5Ce_0.5O₂/SiC. The Pd/Zr_0.5Ce_0.5O₂/SiC catalyst can ignite the reaction at 240 °C and obtain a methane conversion of 100% at 340 °C, and keep 100% methane conversion after 10 reaction cycles. These results indicate that active metallic nanoparticles are well stabilized on the SiC surface while the promoters serve as oxygen reservoir and retain good redox properties.     

Synthesis of highly crystalline spinel LiMn2O4 by a soft chemical route and its electrochemical performance

Highly crystalline spinel LiMn₂O₄ was successfully synthesized by annealing lithiated MnO₂ at a relative low temperature of 600 °C, in which the lithiated MnO₂ was prepared by chemical lithiation of the electrolytic manganese dioxide (EMD) and LiI. The LiI/MnO₂ ratio and the annealing temperature were optimized to obtain the pure phase LiMn₂O₄. With the LiI/MnO₂ molar ratio of 0.75, and annealing temperature of 600 °C, the resulting compounds showed a high initial discharge capacity of 127 mAh g⁻¹ at a current rate of 40 mAh g⁻¹. Moreover, it exhibited excellent cycling and high rate capability, maintaining 90% of its initial capacity after 100 charge-discharge cycles, at a discharge rate of 5 C, it kept more than 85% of the reversible capacity compared with that of 0.1 C.     

Combustion synthesis and characterization of Cu-Sm co-doped CeO2 electrolytes

Nano-sized CSO (Ce_0.80Sm_0.20O_2−δ) and CSCO (Ce_0.79Sm_0.20Cu_0.01O_2−δ) were synthesized by the PVA assisted combustion method, and then characterized by the structure of PVA-cation complexes and nano-powders, as well as mechanical and electrical performance after sintering. The results indicate that the PVA-cation complexes (PVA-(Ce³⁺,Sm³⁺) and PVA-(Ce³⁺,Sm³⁺,Cu²⁺)) were formed by coordinating metal cations to hydroxyl groups, as well as the COO⁻¹ group derived from the oxidation of PVA with NO₃⁻¹. Low temperatures (around 200 °C) caused intense combustion reactions, resulting in the direct crystallization of cubic fluorite nano-CSO (10-20 nm) and nano-CSCO (10-15 nm) crystals with homogeneous element distribution. This slight compositional modification of CSO by co-doping with 1 mol% CuO resulted in a significantly lowered densification temperature, as well as enhanced mechanical and electrical property. The strength improvement can be ascribed to the dense and fine-grained microstructure without normal grain coarsening, resulting in a transgranular-dominant fracture mode during strength testing.     

Structural and optical properties of Tm:Y2O3 transparent ceramic with La2O3, ZrO2 as composite sintering aid

The paper reports the use of La₂O₃ and ZrO₂ co-doping as a composite sintering aid for the fabrication of Tm:Y₂O₃ transparent ceramics. Two groups of experiments were conducted for investigating the influences of composite sintering aids on the microstructures and the optical properties of Tm:Y₂O₃ transparent ceramics in contrast to single La³⁺ and single Zr⁴⁺ doped Tm:Y₂O₃. Samples with composite sintering aids could realize fine microstructures and good optical properties at relatively low sintering temperatures. Grain sizes around 10 μm and transmittances close to theoretical value at wavelength of 2 μm were achieved for the 9 at.% La³⁺, 3 at.% Zr⁴⁺ co-doped samples sintered at 1500-1600 °C. The influences of the composite sintering aids on the emission intensities and the phonon energies of Tm:Y₂O₃ ceramics were also investigated.     

Indirect cathodic electrocatalytic degradation of dimethylphthalate with PW11O39Fe(III)(H2O) and H2O2 in neutral aqueous medium

Cyclic voltammetry and degradation of dimethylphthalate (DMP) revealed that the iron-substituted heteropolytungstate anion PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ is an excellent indirect cathodic oxidative electrocatalyst in the presence of H₂O₂. PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ can electrocatalyze the reduction of H₂O₂ to hydroxyl radicals via an inner-sphere electron transfer mechanism, which cause oxidative decomposition of DMP. Almost complete DMP removal and ca. 30% mineralization were obtained in less than 120 min in a mixed phosphate solution at pH 6.86 containing 0.1 mM DMP. MS analyses of the intermediates and final products suggested that glyoxal, oxalic acid and acetic acid are the main ring-opening products, besides some unstable hydroxylated aromatic intermediates. The effects of added H₂O₂ concentration, applied cathodic potential and DMP initial concentration on the degradation of DMP were also investigated. A concentration of 1.0 mM H₂O₂ and cathodic potential of −0.3 V were optimal conditions for DMP degradation in our experiments. At higher initial DMP concentrations degradation also occurred, but at a slower decay rate compared to lower initial concentrations. The present system thus represents a possible method to use PW₁₁O₃₉Fe(III)(H₂O)⁴⁻ as an indirect cathodic oxidative electrocatalyst in water and wastewater treatment.     

Gold nanoparticles mediate the assembly of manganese dioxide nanoparticles for H2O2 amperometric sensing

Aggregates of gold nanoparticles (AuNPs) that mediate the assembly of manganese dioxide nanoparticles (nano-MnO₂) for hydrogen peroxide (H₂O₂) amperometric sensing have been developed. The aggregates were prepared by directly mixing citric-capped AuNPs and poly(allylamine hydrochloride) (PAH)-capped nano-MnO₂ using an electrostatic self-assembly strategy. The prepared sensor exhibited excellent electrochemical behaviors and a wide linear range from 7.80 × 10⁻⁷ to 8.36 × 10⁻⁴ M with a detection limit of 4.68 × 10⁻⁸ M (S/N = 3) because of the synergistic influence of excellent catalytic ability of MnO₂ and good electrical conductivity of AuNPs. In addition, its applicability to practical samples for measuring H₂O₂ in toothpastes has obtained a satisfactory result. Due to the ease of preparation and excellent properties of the sensor, indicating the MnO₂-AuNP material may be a potential H₂O₂ sensor.     

Hexacyanoferrate ion adsorbed on propylpyridiniumsilsesquioxane polymer film-coated SiO2/Al2O3: use in an electrochemical oxidation study of cysteine

Hexacyanoferrate ion, [Fe(CN)₆]⁴⁻, was immobilized by an ion-exchange reaction on the propylpyridiniumsilsesquioxane chloride polymer thin-film-coated SiO₂/Al₂O₃ surface. The amount of [Fe(CN)₆]⁴⁻ immobilized was 0.22 mmol g⁻¹ with a surface coverage of 9.6×10⁻⁶ mmol cm⁻². A carbon paste electrode made with this material was prepared and its electrochemical properties studied. The electrode presented two well-defined redox peaks with midpoint potentials, E_m, of 0.152 V vs SCE. This potential was not significantly affected by pH changes between 2 and 9.5. The electrode showed much reproducible responses and was successfully used to study the electrochemical oxidation of cysteine.     

Molten salt synthesis of spherical LiNi0.5Mn1.5O4 cathode materials

This paper describes a novel simple redox process for synthesizing monodispersed MnO₂ powders and preparation of spherical LiNi_0.5Mn_1.5O₄ cathode materials by molten salt synthesis (MSS) method. Monodispersed MnO₂ powders have been synthesized by using potassium permanganate and manganese sulfate as the starting materials. By using this redox method, it was found that monodispersed MnO₂ powders with average particle size ∼5 μm can be easily obtained. Resultant MnO₂ and LiOH, Ni(OH)₂ was then used to synthesis LiNi_0.5Mn_1.5O₄ cathode materials with retention of spherical particle shape by MSS method. The discharge capacity was 129 mAh g⁻¹ in the first cycle and 127 mAh g⁻¹ after 50 cycles under an optimal synthesis condition for 12 h at 800 °C.     

Tunable luminescence properties and efficient energy transfer in Eu,Mn co-doped Ba2MgP4O13

A series of Ba₂Mg_1−xMn_xP₄O₁₃ (x = 0-1.0) and Ba_1.94Eu_0.06Mg_1−xMn_xP₄O₁₃ (x = 0-0.15) phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), the photoluminescence spectra, and the decay curves are investigated. XRD analysis shows that the maximum tolerable substitution of Mn²⁺ for Mg is about 50 mol% in Ba₂MgP₄O₁₃. Mn²⁺-singly doped Ba₂MgP₄O₁₃ shows weak red-luminescence peaked at about 615 nm. The Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 430 nm originating from Eu²⁺ and a broad red-emitting one peaked at 615 nm from Mn²⁺ ions. The luminescence of Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ in Ba₂MgP₄O₁₃. The efficient energy transfer from Eu²⁺ to Mn²⁺ is verified by the excitation and emission spectra together with the luminescence decay curves. The emission colors could be tuned from the blue to the red-purple and eventually to the deep red. The resonance-type energy transfer via a dipole-quadrupole interaction mechanism is supported by the decay lifetime data. The energy transfer efficiency and the critical distance are calculated and discussed. The temperature dependent luminescence spectra of the Eu²⁺/Mn²⁺ co-doped phosphor show a good thermal stability on quenching effect.     

High capacity ZnFe2O4 anode material for lithium ion batteries

A nanostructured ternary transition metal oxide, ZnFe₂O₄, is synthesized via the simple polymer pyrolysis method. The characteristics of the material are examined by thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The electrochemical test results show that this method of ZnFe₂O₄ synthesis produces high specific capacities and good cycling performance, with an initial specific capacity as high as 1419.6 mAh g⁻¹ at first discharge that is maintained at over 800 mAh g⁻¹ even after 50 charge–discharge cycles. The electrode also presents a good rate capability, with a high rate of 4C (1C = 928 mA g⁻¹), a reversible specific capacity that can be as high as 400 mAh g⁻¹. ZnFe₂O₄ is a potential alternative to high-performance nanostructured anode material in lithium ion batteries.     

Inactivation of Escherichia coli in Na2SO4 electrolyte using boron-doped diamond anode

Electrochemical disinfection in chloride-free electrolyte has attracted more and more attention due to advantages of no production of disinfection byproducts (DBPs), and boron-doped diamond (BDD) anode with several unique properties has shown great potential in this field. In this study, inactivation of Escherichia coli (E. coli) was investigated in Na₂SO₄ electrolyte using BDD anode. Firstly, disinfection tests were carried on at different current density. The inactivation rate of E. coli and also the concentration of hydroxyl radical (OH) increased with the current density, which indicated the major role of OH in the disinfection process. At 20 mA cm⁻² the energy consumption was the lowest to reach an equal inactivation. Moreover, it was found that inactivation rate of E. coli rose with the increasing Na₂SO₄ concentration and they were inactivated more faster in Na₂SO₄ than in NaH₂PO₄ or NaNO₃ electrolyte even in the presence of OH scavenger, which could be attributed to the oxidants produced in the electrolysis of SO₄²⁻, such as peroxodisulfate (S₂O₈²⁻). And the role of S₂O₈²⁻ was proved in the disinfection experiments. These results demonstrated that, besides hydroxyl radical and its consecutive products, oxidants produced in SO₄²⁻ electrolysis at BDD anode played a role in electrochemical disinfection in Na₂SO₄ electrolyte.     

Greatly improved elevated-temperature cycling behavior of Li1+xMgyMn2−x−yO4+δ spinels with controlled oxygen stoichiometry

A new type of oxygen stoichiometric and Mg-doped LiMn₂O₄ spinel with improved crystallinity and decreased surface area was synthesized by a special “two-step” method: first, calcinate the mixture of metal oxides at “ultra-high” temperatures (950-1100 °C) to obtain an intermediate product with improved crystallinity, larger particle size and oxygen defects; then, anneal the intermediate at relatively low temperatures (600-800 °C) with the addition of extra LiOH to achieve oxygen stoichiometry. These spinels with general formula Li_1+xMg_yMn_2−x−yO_4+δ or (Li, Mg, Mn)₃O_4+δ are oxygen-rich based on chemical analysis (O/(Li+Mg+Mn) ratio larger than 4:3), and they can be called oxygen stoichiometric spinels with metal cation vacancies and rewritten as [Li]_8a[Li_nMg_mMn_{2−n−m−p}□_p]_16d[O₄]_32e. This new kind of materials with controlled oxygen stoichiometry exhibited greatly improved cycling performance and reduced Mn dissolution at elevated temperatures over that of other Mg-doped materials prepared by conventional “one-step” method.     

Double channel electrode flow cell application to the study of HO2 production on MnxCo3−xO4 (0 ≤ x ≤ 1) spinel films

We conducted a study on the electroreduction of O₂ in alkaline solution at room temperature on pure thin oxide electrodes of composition Mn_xCo_3−xO₄ (0 ≤ x ≤ 1) using the double channel electrode flow cell (DCEFC). The oxides were prepared at 150 °C and deposited by spray pyrolysis onto titanium substrates. The oxygen reduction reaction (orr) occurs through “interactive” and “parallel” pathways, and the ratio of O₂ molecules reduced to OH⁻ ions with respect to those reduced to HO₂⁻ ions depends on the oxide stoichiometry and on the applied overpotential. The formation of HO₂⁻ increases when the manganese concentration increases. The results obtained for the orr show that the number of electrons transferred per O₂ molecule decreases from 3 to 2 and the ratio k₁/k₂ (the rate constants for direct reduction to OH⁻ and indirect reduction to HO₂⁻) increases, respectively, in the overpotential studied range (−0.05 to −0.6 V). The Mn³⁺ ions placed in the B-sites of the spinel structure seem to be the active centres, where hydrogen peroxide is formed.     

Electrocatalytic oxidation of ascorbic acid by [Fe(CN)6] redox couple electrostatically trapped in cationic N,N-dimethylaniline polymer film electropolymerized on diamond electrode

Multinegatively charged metal complex, hexacyanoferrate ([Fe(CN)₆]⁴⁻), was electrostatically trapped in the cationic polymer film of N,N-dimethylaniline (PDMA) which was electrochemically deposited on the boron-doped diamond (BDD) electrode by controlled-potential electro-oxidation of the monomer. This ferrocyanide-trapped PDMA film was used to catalyze the oxidation of ascorbic acid (AA). Increase in the oxidation current response with a negative shift of the anodic peak potential was observed at the cationic PDMA film-coated BDD (PDMA|BDD) electrode, compared with that at the bare BDD electrode. A more drastic enhancement in the oxidation peak current as well as more negative shift of oxidation potential was found at the ferrocyanide-trapped PDMA film-coated BDD ([Fe(CN)₆]^3−/4−|PDMA|BDD) electrode. This [Fe(CN)₆]^3−/4−|PDMA|BDD electrode can be used as an amperometric sensor of AA. Ferrocyanide, electrostatically trapped in the polymer film shows more electrocatalytic activity than that coordinatively attached to the polymer film or dissolved in the solution phase. The electrocatalytic current depends on the surface coverage of ferricyanide, Γ_Fe, within the polymer film. Diffusion coefficient (D) of AA in the solution was estimated by rotating disk electrode voltammetry: D = (5.8 ± 0.3) × 10⁻⁶ cm² s⁻¹. The second-order rate constant for the catalytic oxidation of AA by ferricyanide was also estimated to be 9.0 × 10⁴ M⁻¹ s⁻¹. In the hydrodynamic amperometry using the [Fe(CN)₆]^3−/4−|PDMA|BDD electrode, a successive addition of 1 μM AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.233 μA cm⁻² μM⁻¹.