Hydrogen peroxide induced formation of peroxystannate nanoparticles

Stable, amorphous potassium peroxystannate nanoparticles of controlled average size—in the range 10–100 nm—and of controlled hydrogen peroxide content—in the range of 19–30 wt%—were synthesized by hydrogen peroxide induced polymerization in water–potassium hexahydroxostannate solutions. The sol phase and the precipitate were characterized by vibrational spectroscopies, ¹¹⁹Sn NMR, XPS and XRD using crystalline K₂Sn(OH)₆ and K₂Sn(OOH)₆ reference materials. This is the first study to show that peroxocoordination induces polymerization of a main group element. ¹¹⁹Sn NMR studies show that peroxotin coordination and polymerization took place already in the hydrogen peroxide–water phase. The high abundance of peroxotin bonds revealed by ¹¹⁹Sn MAS NMR, vibrational spectroscopy, and XPS suggests that the particles are predominantly made of peroxo bridged tin networks. Although the particles are highly stable in the dry phase as well as in alcohol solutions and do not lose hydrogen peroxide upon storage, they release their stored hydrogen peroxide content by exposure to water.     

Neubestimmung der Kristallstrukturen der Hexahydroxometallate Na2Sn(OH)6, K2Sn(OH)6 und K2Pb(OH)6

Redetermination of the Crystal Structures of the Hexahydroxometallates Na₂Sn(OH)₆, K₂Sn(OH)₆, and K₂Pb(OH)₆ Slow cooling down of hot saturated hydroxo stannate‐ resp. ‐plumbate solutions gives crystals of Na₂Sn(OH)₆, K₂Sn(OH)₆, and K₂Pb(OH)₆ well suited for an X‐ray structure determination. With these crystals the so far known crystal data were verified, determined more precisely and H‐positions found for the first time. The compounds crystallize rhombohedral in the space group R 3. The hexagonal unit cells contain three formula units with Na₂Sn(OH)₆: a = 5.951(1) Å, c = 14.191(2) Å, c/a = 2.384 K₂Sn(OH)₆: a = 6.541(1) Å, c = 12.813(4) Å, c/a = 1.959 K₂Pb(OH)₆: a = 6.625(1) Å, c = 12.998(2) Å, c/a = 1.962 The compounds are not isotypic whereas the atoms occupy in all three cases the same Wyckoff positions. Na₂Sn(OH)₆ has with an hcp packing of O a CdI₂ like superstructure with Na and Sn in octahedral interstices. Hydrogen bonds O–H…O–H play a role in solid K₂Sn(OH)₆ and K₂Pb(OH)₆. In these compounds the potassium ions are shifted from an octahedral coordination in an hcp packing of O. They have nine nearest O‐neighbours. The hydrogen bonds are investigated by Raman spectroscopy.     

Photocatalytic Hydrogen Production by the Sensitization of Sn(IV)-Porphyrin Embedded in a Nafion Matrix Coated on TiO2

Efficient utilization of visible light for photocatalytic hydrogen production is one of the most important issues to address. This report describes a facile approach to immobilize visible-light sensitizers on TiO₂ surfaces. To effectively utilize the sensitization of Sn(IV) porphyrin species for photocatalytic hydrogen production, perfluorosulfonate polymer (Nafion) matrix coated-TiO₂ was fabricated. Nafion coated-TiO₂ readily adsorbed trans-diaqua[meso-tetrakis(4-pyridinium)porphyrinato]tin(IV) cation [(TPy^HP)Sn(OH₂)₂]⁶⁺ via an ion-exchange process. The uptake of [(TPy^HP)Sn(OH₂)₂]⁶⁺ in an aqueous solution completed within 30 min, as determined by UV-vis spectroscopy. The existence of Sn(IV) porphyrin species embedded in the Nafion matrix coated on TiO₂ was confirmed by zeta potential measurements, UV-vis absorption spectroscopy, TEM combined with energy dispersive X-ray spectroscopy, and thermogravimetric analysis. Sn(IV)-porphyrin cationic species embedded in the Nafion matrix were successfully used as visible-light sensitizer for photochemical hydrogen generation. This photocatalytic system performed 45% better than the uncoated TiO₂ system. In addition, the performance at pH 7 was superior to that at pH 3 or 9. This work revealed that Nafion matrix coated-TiO₂ can efficiently produce hydrogen with a consistent performance by utilizing a freshly supplied cationic Sn(IV)-porphyrin sensitizer in a neutral solution.     

A facile carbothermal preparation of Sn–Co–C composite electrodes for Li-ion batteries using low-cost carbons

Sn–Co–C composites were prepared by carbothermal reaction of ball-milled precursors. X-ray diffraction and ¹¹⁹Sn Mössbauer spectroscopy of the original composites revealed the predominance of Sn and CoSn₂ phases for those samples prepared with a high Sn/Co ratio. Electron microscopy images showed a homogeneous dispersion of sub-micrometric metallic particles in the carbon matrix. Galvanostatic cycling at several kinetic rates revealed that Sn₇Co₁C₉₂ and Sn₈Co₄C₈₈ are able to maintain 400 mA h g^?1 after 40 cycles at 35 mA g^?1. The large CoSn₂ contribution revealed by Mössbauer spectroscopy in the original and cycled electrodes is responsible for the good electrochemical performance. This interpretation is also supported by impedance spectroscopy measurements.     

Effect of the hydrogen peroxide concentration in stereospecific oxidation of alkanes by models of non-heme oxygenases

The biomimetic oxidation of alkanes (cyclohexane, adamantane, cis-1,2-dimethylcyclohexane) with hydrogen peroxide catalyzed by Fe(II) complexes containing tetradentate nitrogen ligands (M = [Fe(bpmen)(MeCN)₂](ClO₄)₂ (bispicolyl-1,2-dimethylethylenediamine), [Fe(bpen)(MeCN)₂](ClO₄)₂ (bispicolylethylenediamine), and [Fe(tpcaH)(MeCN)₂]₂(ClO₄)₄ (tripyridylcarboxamide) is studied. The effects of the hydrogen peroxide concentration on the alcohol/ketone (A/K) ratio and on the regioselectivity of oxidation (3/2) are discovered. Rather high stereospecificity (RC = 96–99%) persisting at high hydrogen peroxide concentrations is hardly consistent with the participation of the HO^. radical, inferred from the rather low regioselectivity and low A/K ratio observed under these conditions. The molecular mechanism of oxygen transfer from hydrogen peroxide, which was earlier proved reliably for low concentrations of hydrogen peroxide ([H₂O₂]/[M] ? 10), can be applied to high peroxide concentrations ([H₂O₂]/[M] > 10) if a new ferryl species containing two equivalents of the oxidant is assumed to be involved in the process. This assumption is confirmed by the direct stereospecific formation of alkyl hydroperoxide from alkane at a high concentration of hydrogen peroxide.     

Study of tin dioxide–sodium stannate composite obtained by decomposition of peroxostannate as a potential anode material for lithium-ion batteries

A tin dioxide–sodium stannate composite has been obtained by the thermal treatment of sodium peroxostannate nanoparticles at 500°C in air. X-ray powder diffraction study has revealed that the composite includes crystalline phases of cassiterite SnO₂, sodium stannate Na₂Sn₂O₅, and sodium hexahydroxostannate Na₂Sn(OH)₆. Scanning electron microscopy has shown that material morphology does not change considerably as compared with the initial tin peroxo compound. Electrochemical characteristics have been compared for the anodes of lithium-ion batteries based on tin dioxide–sodium stannate composite and anodes based on a material manufactured by the thermal treatment of graphene oxide–tin dioxide–sodium stannate composite at 500°C in air.     

Hemoglobin co-immobilized with silver–silver oxide nanoparticles on a bare silver electrode for hydrogen peroxide electroanalysis

Hemoglobin (Hb) and silver–silver oxide (Ag–Ag₂O) nanoparticles were co-immobilized on a bare silver electrode surface by cyclic voltammetry, and were characterized by UV–vis reflection spectroscopy, scanning electron microscopy, and electrochemical impedance spectroscopy. The immobilized Hb was shown to maintain its biological activity well. Direct electron transfer between Hb and the resulting electrode was achieved without the aid of any electron mediator. The reduction currents to hydrogen peroxide (H₂O₂) at co-immobilized electrodes showed a linear relationship with H₂O₂ concentration over a concentration range from 6.0?×?10^?6 to 5.0?×?10^?2 mol L^?1, and a detection limit of 2.0?×?10^?6 mol L^?1 (S/N?=?3).     

Organtin complexes of 2,5‐dithiobiurea (H2dtbu): The crystal structures of (Ph3Sn)2(dtbu) and [(n‐Bu)2SnCl]2(dtbu)

A series of organotin(IV) complexes of two types, [R₃Sn]₂(dtbu) (R = PhCH₂ 1 , Ph 2 , n‐Bu 3 , H₂dtbu = 2,5‐dithiobiurea), [R₂SnCl]₂(dtbu) (R = PhCH₂ 4 , Ph 5 , n‐Bu 6 ) have been synthesized and characterized by elemental analysis, IR, and NMR (¹H, ¹¹⁹Sn) spectroscopy. The structures of 2 and 6 have been determined by X‐ray crystallography. Crystal structures show that both complexes 2 and 6 are the symmetric dinuclear unit. Interestingly, supramolecular structures show that complex 2 has formed a linear chain through N H⋅⋅⋅S hydrogen bonding and 6 has formed a two‐dimensional network in perfect bc plane connected through N H⋅⋅⋅Cl hydrogen bonding and nonbonded S⋅⋅⋅S interactions. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:435–442, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20456     

Heterotermetallic Indium Lithium Halostannates: Low‐Temperature Single‐Source Precursors for Tin‐Rich Indium Tin Oxides and Their Application for Thin‐Film Transistors

The syntheses and structural elucidation of dimeric [Sn(OCyHex)₂] ( 1 ), its corresponding (cyclohexoxy)alkalistannates(II) [{M(OCyHex)₃Sn}₂] (M=Li ( 2 ), Na ( 3 ), K ( 4 )), and of the first heteroleptic heterotermetallic Li/In/Sn–haloalkoxide clusters [X₂In{LiSn₂(OCyHex)₆}] (X=Br ( 5 ), Cl ( 6 )) with a double seco‐norcubane core are reported. They represent suitable precursors for new amorphous indium tin oxide (ITO) materials as transparent conducting oxides with drastically reduced concentrations of expensive indium, while maintaining their high electrical performance. In fact, compounds 5 and 6 were successfully degraded under dry synthetic air at relatively low temperature, resulting in new semiconducting tin‐rich ITOs homogeneously dispersed in a tin oxide/lithium oxide matrix. The obtained particles were investigated and characterised by different analytical techniques, such as powder XRD, IR spectroscopy, SEM, TEM and energy‐dispersive X‐ray spectroscopy (EDX). The analytical data confirm that the final materials consist of tin‐containing indium oxide embedded in an amorphous tin oxide matrix. The typical broadening and shift of the observed indium oxide reflections to higher 2θ values in the powder XRD pattern clearly indicated that tin centres were successfully incorporated into the In₂O₃ lattice and partially occupied In³⁺ sites. Investigations by EDX mapping proved that Sn was homogeneously distributed in the final materials. Thin‐film field‐effect transistors (FETs) were fabricated by spin‐coating of silicon wafers with solutions of 5 in toluene and subsequent calcination under dry air (25–700 °C). The FETs prepared with precursor 5 exhibited excellent performances, as shown by a charge‐carrier mobility of 6.36×10^?1 cm² V^?1 s (calcination at 250 °C) and an on/off current ratio of 10⁶.     

A Novel Fluorescent Reagent for Analysis of Hydrogen Peroxide

IntroductionTheoxidationofmanyclinicalsubstancesinbodyfluidsproducesaquantityofhydrogenperoxide ,sothedetermina tionoftracehydrogenperoxideisofconsiderableimportanceinclinicalchemistry .1Further,themonitoringofhydrogenperoxideisalsonecessarytoenvironmentalsciencesinceitisakeyspeciesinthereactionsofthetroposphere,beingin volvedinimportantreactionssuchasthecatalyzedoruncat alyzedaqueousphaseoxidationofSO2 andtheultraviolet en hancedaqueousphaseoxidationoforganicspecies.2 Uptonow ,variousmethods…     

Efficient and Reusable Sn(II)‐containing Imidazolium‐based Ionic Liquid as a Catalyst for the Oxidation of Benzyl Alcohol

A simple and efficient catalytic system [BBIM]Br–SnCl₂ for the oxidation of benzyl alcohol using hydrogen peroxide as the oxidant has been developed. Reaction conditions such as the catalyst dose, the solvents, reaction temperature, reaction time, and the amount of hydrogen peroxide were investigated. The optimum reaction conditions identified were 0.11 g of catalyst, no solvent, 65°C, 15 min, and 2 mmol of hydrogen peroxide. Oxidation of various alcohols was also investigated under the optimized conditions. The catalyst [BBIM]Br–SnCl₂ can be easily recovered and reused for six reaction runs without significant loss of catalytic activity, because the Sn species of the catalyst can be coordinated with the imidazole ring of the ionic liquid. The reused catalyst was further characterized by Fourier transform infrared spectroscopy to evaluate its chemical properties. The results proved that the [BBIM]Br–SnCl₂ catalyst was stable and reusable for the oxidation reactions. A possible mechanism for the oxidation of benzyl alcohol to benzaldehyde is proposed.     

Study and application of the complex of Sn(II) with glycerol in volumetric analysis

The preparation of standard Sn(II) solutions in glycerol and ethanol media was studied and the most suitable conditions were found for their standardization using dichromate and potassium hexacyanoferrate. Further, the long-term stability of standard Sn(II)-glyc solutions was studied and it was found that the titer of 0.1 N Sn(II)-glyc does not change in an inert atmosphere over a period of 4 months. The solution undergoes partial oxidation in the air (Fig. 1). It was demonstrated polarographically and voltammetrically that the studied redox system is irreversible. The formal redox potential value E_f⁰ = 0.80 V (SCE) 0.1 N Sn(II)-glyc can be back-titrated with 0.1 N K₂Cr₂O₇ in a sat. Na₂CO₃ solution under an inert atmosphere. Generally it is possible in sat. Na₂CO₃ medium to determine with great precision dichromate and potassium hexacyanoferrate, iodine, chloramine-T, chlorine lime, hydrogen peroxide, inorganic peroxides, and silver (Table 2). Equilibrium potentiometry, bipotentiometry, and biamperometry can be used for indication of the equivalence point.     

Drum-shaped mono-organooxotin assembly through solvothermal synthesis with 2,3,4,5-tetrafluorobenzoic acid: crystal structure,hydrogen bonding and π–π stacking interactions

A drum-shaped organooxotin (IV) complex with 2,3,4,5-tetrafluorobenzoic acid of the type {[SnR₂(2,3,4,5-F₄C₆HCO₂)]O}₆ (R?=?m-Cl-PhCH₂) has been solvothermally synthesized and structurally characterized by elemental, IR, ¹H, ¹³C, ¹¹⁹Sn NMR spectra and X-ray crystallography diffraction analysis. This complex exhibits a new structural environment appearing as a “drum” arrangement with hexa-coordinated tin atoms in a four-membered stannoxane ring, (–Sn–O–)₂, as a common structural feature. Each tin(IV) displays a distorted octahedral geometry. Weak, but significant, intramolecular C–H?···?F hydrogen bonds and π–π stacking interactions are shown. These contacts lead to aggregation and supramolecular self-assembly. Cleavage of Sn–C bond occurred in complexes under the influence of strong acid.     

Syntheses and structural characterization of organotin complexes derived from 2-(trifluoromethyl)benzeneseleninic acid: tetranuclear macrocycle, 1-D polymeric chain,helical double-chain

Four organotin(IV) complexes based on 2-(trifluoromethyl)benzeneseleninic acid, [Me₃Sn(O₂SeC₆H₄-2-CF₃)]₄ (1), [Ph₃Sn(O₂SeC₆H₄-2-CF₃)]_n (2), [R₂Sn(O₂SeC₆H₄-2-CF₃)₂]_n (R = Me 3; n-Bu 4), have been synthesized and characterized by X-ray diffraction, elemental analysis, infrared spectroscopy, and NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy. Single-crystal X-ray analyses show that 1 has a centrosymmetric tetranuclear triorganotin selenite with a tetranuclear 16-membered macrocycle formed by trimethyltin and ligand alternately linking; 2 exhibits a 1-D neutral infinite chain structure in which the [O₂SeC₆H₄-2-CF₃]^? is a μ₂-bridging ligand; 3 and 4 are polymeric chain structures containing Sn₂O₄Se₂ eight-membered rings where the areneseleninate groups are double bridges between the tin ions. Examination of the intermolecular contacts of 1 reveals the existence of the C–H?O hydrogen bonding interactions and C–H?π interactions. Weak C–H?O interactions were also found to be important for the formation of the 3-D structure for 3.     

Flow injection determination of hydrogen peroxide using diperiodatoargentate- and diperiodatonickelate-luminol chemiluminescence

A novel chemiluminescence (CL) method for the determination of hydrogen peroxide is described. Method is based on the transition metals in highest oxidation state complex, which include diperiodatoargentate (DPA) and diperiodatonickelate (DPN) and show excellent sensitisation on the luminol-H₂O₂ CL reaction with low luminol concentration in alkaline medium. In particular, the sensitiser which was previously reported (such as Co²⁺, Cu²⁺, Ni²⁺, Mn²⁺, Fe³⁺, Cr³⁺, KIO₄, K₃Fe(CN)₆ etc.) to be unobserved CL due to poor sensitisation with such low concentration of luminol which makes the method hold high selectivity. Based on this observation, the detection limits were 6.5?×?10^?9?mol?L^?1 and 1.1?×?10^?8?mol?L^?1 hydrogen peroxide for the DPN- and DPA-luminol CL systems, respectively. The relative CL intensity was linear with the hydrogen peroxide concentration in the range of 2.0?×?10^?8–6.0?×?10^?6?mol?L^?1 and 4.0?×?10^?8–4.0?×?10^?6?mol?L^?1 for the DPN- and DPA-luminol CL systems, respectively. The proposed method had good reproducibility with a relative standard deviation of 3.4% (8.0?×?10^?7?mol?L^?1, n?=?7) and 1.0% (2.0?×?10^?6?mol?L^?1, n?=?7) for the DPN- and DPA-luminol CL systems, respectively. A satisfactory result has been gained for the determination of H₂O₂ in rainwater and artificial lake water by use of the proposed method.     

The kinetics of complex formation between Ti(IV) and hydrogen peroxide

The kinetics of the formation of the titanium‐peroxide [TiO²⁺₂] complex from the reaction of Ti(IV)OSO₄ with hydrogen peroxide and the hydrolysis of hydroxymethyl hydroperoxide (HMHP) were examined to determine whether Ti(IV)OSO₄ could be used to distinguish between hydrogen peroxide and HMHP in mixed solutions. Stopped‐flow analysis coupled to UV‐vis spectroscopy was used to examine the reaction kinetics at various temperatures. The molar absorptivity (ε) of the [TiO²⁺₂] complex was found to be 679.5 ± 20.8 L mol^?1 cm^?1 at 405 nm. The reaction between hydrogen peroxide and Ti(IV)OSO₄ was first order with respect to both Ti(IV)OSO₄ and H₂O₂ with a rate constant of 5.70 ± 0.18 × 10⁴ M^?1 s^?1 at 25°C, and an activation energy, E_a = 40.5 ± 1.9 kJ mol^?1. The rate constant for the hydrolysis of HMHP was 4.3 × 10^?3 s^?1 at pH 8.5. Since the rate of complex formation between Ti(IV)OSO₄ and hydrogen peroxide is much faster than the rate of hydrolysis of HMHP, the Ti(IV)OSO₄ reaction coupled to time‐dependent UV‐vis spectroscopic measurements can be used to distinguish between hydrogen peroxide and HMHP in solution. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 457–461, 2007     

Direct synthesis of hydrogen peroxide from hydrogen and oxygen over insoluble Pd<Subscript>0.15</Subscript>M<Subscript>2.5</Subscript>H<Subscript>0.2</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript> (M = K,Rb, and Cs) heteropolyacid catalysts

Palladium-containing insoluble heteropolyacid (HPA) catalysts (Pd_0.15M_2.5H_0.2PW₁₂O₄₀) were prepared by an ion-exchange method using various alkaline metal ions (M = K⁺, Rb⁺, and Cs⁺) (denoted as Pd-KPW, Pd-RbPW, and Pd-CsPW). They were then applied to the direct synthesis of hydrogen peroxide from hydrogen and oxygen. Conversion of hydrogen over the catalysts was almost identical with no great difference, while selectivity for hydrogen peroxide increased in the order of Pd-KPW < Pd-RbPW < Pd-CsPW. As a consequence, yield for hydrogen peroxide increased in the order of Pd-KPW < Pd-RbPW < Pd-CsPW. It was found that yield for hydrogen peroxide increased with increasing Pd 3d_5/2 binding energy of the catalyst. Among the catalysts tested, Pd-CsPW catalyst with the highest Pd 3d_5/2 binding energy showed the highest yield for hydrogen peroxide.     

Relationship Between the J(Sn–C–H) of the Dimethyltin Dichloride Adducts of some Pyridines and Anilines,and the Donor Strength of the Lewis Bases

A study by titrimetric methods of the donor strength of pyridine and aniline and some of their para -substituted derivatives, and the J (¹¹⁹Sn–C–H) of their adducts with dimethyltin dichloride in nitrobenzene, has shown that the p K _b of a Lewis base and its para -substituted derivatives varies linearly with the J (¹¹⁹Sn–C–H) of the adducts of dimethyltin dichloride (Me₂SnCl₂), with the Lewis base dissolved in an inert solvent. A graphical plot of the p K _b of a given series of Lewis bases versus the J (Sn–C–H) of their complexes with Me₂SnCl₂ in nitrobenzene (at the same temperature, and same complex concentration) gives a straight line with a negative gradient, making possible the deduction of the other parameter (e.g. p K _b) for a Lewis base in the series, where the one parameter (e.g. J (Sn–C–H) is known. The graph for each series of Lewis base has its own characteristic gradient, and the gradients appear proportional in magnitude to the donor strengths of each class of the bases, making it possible to deduce from such graphs which series of Lewis bases are the stronger donors.     

Facile Mechanochemical Synthesis of Nano SnO2/Graphene Composite from Coarse Metallic Sn and Graphite Oxide: An Outstanding Anode Material for Lithium‐Ion Batteries

A facile method for the large‐scale synthesis of SnO₂ nanocrystal/graphene composites by using coarse metallic Sn particles and cheap graphite oxide (GO) as raw materials is demonstrated. This method uses simple ball milling to realize a mechanochemical reaction between Sn particles and GO. After the reaction, the initial coarse Sn particles with sizes of 3–30 μm are converted to SnO₂ nanocrystals (approximately 4 nm) while GO is reduced to graphene. Composite with different grinding times (1 h 20 min, 2 h 20 min or 8 h 20 min, abbreviated to 1, 2 or 8 h below) and raw material ratios (Sn:GO, 1:2, 1:1, 2:1, w/w) are investigated by X‐ray diffraction, X‐ray photoelectron spectroscopy, field‐emission scanning electron microscopy and transmission electron microscopy. The as‐prepared SnO₂/graphene composite with a grinding time of 8 h and raw material ratio of 1:1 forms micrometer‐sized architected chips composed of composite sheets, and demonstrates a high tap density of 1.53 g cm^?3. By using such composites as anode material for LIBs, a high specific capacity of 891 mA h g^?1 is achieved even after 50 cycles at 100 mA g^?1.     

Surface modification of FePO4 particles with conductive layer of polypyrrole

Polypyrrole–FePO₄ powder was synthesized by an oxidative polymerization of pyrrole monomer on the surface of FePO₄ powder. The polymerization reaction was initiated using hydrogen peroxide in an acidified solution and catalysed with Fe³⁺. The samples were investigated by light microscopy (LM), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). These methods confirmed the presence of polypyrrole on FePO₄ particles and its homogeneous distribution in the composite material. To determine the PPy content in the PPy–FePO₄ composites a thermogravimetric analysis was used. Cyclic voltammetry curves (CV) were measured and compared in a non-aqueous lithium salt solution for electrodes consisting of pellets made from pure FePO4 and FePO₄/PPy. Electrochemical impedance spectroscopy (EIS) showed that coating of PPy significantly decreases the charge transfer resistance of PPy–FePO₄ electrodes.