Mesoporous solid acid catalysts: relationship between amine TPD data and catalytic activities

The concentrations of surface acid sites on Al³⁺- and H⁺-exchanged AlMCM-41 catalysts have been measured by temperature-programmed desorption (TPD) of a series of primary, secondary and tertiary amines, and by adsorption of ammonia. Surface acid site concentrations have been compared with cation exchange capacities (CECs) and catalytic activities in the alkylation of toluene with benzyl alcohol. The results show that the catalytic activities of the two ion-exchanged forms of the AlMCM-41 are similar. This is reflected in the acid site concentrations measured with tri-n-butylamine, and to a lesser extent tri-i-butylamine, which are similar for both ion-exchanged forms of the catalyst, and close to the CEC. Acid site concentrations measured with smaller amines and ammonia are similar to those based on tributylamine TPD for H⁺-exchanged AlMCM-41, but the Al³⁺ form of the catalyst appears to chemisorb significantly more of the smaller amines and ammonia, resulting in higher than expected acid site concentrations when these adsorbates are used. Larger amines than the tributylamines show very low chemisorption capacities on both forms of AlMCM-41, and appear to access only a small proportion of the surface acid sites. The primary amines tested show poor separation of chemisorbed and physisorbed amine in TPD experiments, making the determination of acid site concentration difficult. The results illustrate the importance of choosing an appropriate amine in using TPD to measure catalyst surface acidities.     

Effect of potassium and silver ion-exchange on the strengthening effect and properties of aluminosilicate glass

In this work, the aluminosilicate glass was subjected to ion-exchange using the KNO₃-AgCl mixed molten salt in order to strengthen the glass while imparting antimicrobial properties. The concentration distribution of K⁺ ions and Ag⁺ ions of the ion-exchanged glasses was characterized by EDS, the effects of ion-exchange temperature (460-500 °C), ion-exchange time (0.5-3 h) and AgCl concentration (0–2.5 wt%) in the mixed molten salt on the strengthening effect and properties of the glass were investigated. The results showed that Ag⁺-Na⁺ ion-exchange, K⁺-Na⁺ ion-exchange existed simultaneously, and Ag⁺-Na⁺ ion-exchange occurred preferentially. Due to the presence of metallic silver, the appearance of the Ag⁺ ion-exchanged glass was light yellow and its transmittance showed a decrease. The surface compressive stress trended up and then down with increasing temperature and time because of the stress relaxation effect. The Vickers hardness of ion-exchanged glass increased by 15%, and the densities and chemical stability were also increased. Ions leaching experiments showed that the Ag⁺ ions release concentration of silver-loaded glass in aqueous environment can reach the bactericidal level. It has been shown that ion-exchange of glass in KNO₃-AgCl mixed molten salts allowed the glass to be strengthened and incorporated with antimicrobial active ions, its chemical stability was improved, too.     

Electrical properties of V2O5–WO3/TiO2 EUROCAT catalysts evidence for redox process in selective catalytic reduction (SCR) deNOx reaction

Electrical conductivity measurements on EUROCAT V₂O₅–WO₃/TiO₂ catalyst and on its precursor without vanadia were performed at 300°C under pure oxygen to characterize the samples, under NO and under NH₃ to determine the mode of reactivity of these reactants and under two reaction mixtures ((i) 2000 ppm NO + 2000 ppm NH₃ without O₂, and (ii) 2000 ppm NO + 2000 ppm NH₃ + 500 ppm O₂) to put in evidence redox processes in SCR deNO_x reaction.It was first demonstrated that titania support contains certain amounts of dissolved W⁶⁺ and V⁵⁺ ions, whose dissolution in the lattice of titania creates an n-type doping effect. Electrical conductivity revealed that the so-called reference pure titania monolith was highly doped by heterovalent cations whose valency was higher than +4. Subsequent chemical analyses revealed that so-called pure titania reference catalyst was actually the WO₃/TiO₂ precursor of V₂O₅–WO₃/TiO₂ EUROCAT catalyst. It contained an average amount of 0.37 at.% W⁶⁺dissolved in titania, i.e. 1.07 × 10²⁰ W⁶⁺ cations dissolved/cm³ of titania. For the fresh catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved in titania were found to be equal to 1.07 × 10²⁰ and 4.47 × 10²⁰ cm⁻³, respectively. For the used catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved were found to be equal to 1.07 × 10²⁰ and 7.42 × 10²⁰ cm⁻³, respectively. Since fresh and used catalysts have similar compositions and similar catalytic behaviours, the only manifestation of ageing was a supplementary progressive dissolution of 2.9 × 10²⁰ additional V⁵⁺ cations in titania.After a prompt removal of oxygen, it appeared that NO alone has an electron acceptor character, linked to its possible ionosorption as NO⁻ and to the filling of anionic vacancies, mostly present on vanadia. Ammonia had a strong reducing behaviour with the formation of singly ionized vacancies. A subsequent introduction of NO indicated a donor character of this molecule, in opposition to its first adsorption. This was ascribed to its reaction with previously adsorbed ammonia strongly bound to acidic sites. Under NO + NH₃ reaction mixture in the absence of oxygen, the increase of electrical conductivity was ascribed to the formation of anionic vacancies, mainly on vanadia, created by dehydroxylation and dehydration of the surface. These anionic vacancies were initially subsequently filled by the oxygen atom of NO. N^o atoms, resulting from the dissociation of NO and from ammonia dehydrogenation, recombined into dinitrogen molecules. The reaction corresponded to

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. In the presence of oxygen, NO did not exhibit anymore its electron acceptor character, since the filling of anionic vacancies was performed by oxygen from the gas phase. NO reacted directly with ammonia strongly bound on acidic sites. A tentative redox mechanism was proposed for both cases.     

Investigations on the CoAPO-36 molecular sieve

Highly crystalline cobalt aluminophosphates of type 36 have been synthesized and characterized. Investigations on the thermal decomposition of Pr₃N-CoAPO-36 and the surface, sorption, acid strength distribution, acidic and catalytic properties of CoAPO-36 were carried out. The XPS analysis indicated that the concentration of cobalt was higher in the bulk of the material than on the surface. The surface of the cobalt aluminophosphate is aluminium rich. The number of strong acid sites is higher on the CoAPO-36 than on CoAPO-5, MAPO-5 and ZAPO-36. The catalytic activities of CoAPO-5, MAPO-5, ZAPO-36, CoAPO-36, MAPO-36 and MAPSO-36 in the 3-methylpentane ando-xylene conversion reactions were compared. The catalytic turnover rate per framework substituted atom in the conversion ofo-xylene for CoAPO-36 is higher than for the MAPO-5, CoAPO-5, ZAPO-36 and MAPSO-36. In the ethylbenzene conversion reaction, the deactivation of the cobalt aluminophosphate and magnesium aluminophosphates of type 36 were studied.     

Aromatization of pentane catalyzed over various metallosilicates

Various metallosilicates were synthesized using a hydrothermal method and characterized by SEM, XRD,²⁹Si MAS NMR, chemical analysis and surface area measurements. These results showed that they had a MFI structure. The pentane aromatization reaction was carried out over these metallosilicates in a continuous flow reactor at 550 °C, He/pentane=3, WHSV=1.5 h⁻¹ and 1 atm. Among the various metallosilicates, [Ga]ZSM-5(20) (52.3%) and [Zn]ZSM-5(40) (37.6%) showed higher aromatic selectivities for pentane aromatization. When [Al] ZSM-5(40) was ion-exchanged with gallium nitrate and zinc chloride, the selectivities for aromatics increased from 23.0% to 35.5% and to 32.7%, respectively. The Si/metal mole ratios of [Ga]ZSM-5 and [Al]ZSM-5 were changed from 20 to 250 and NH₃ temperature programmed desorption (TPD) was carried out. As the Si/metal ratio was changed from 250 to 20, the selectivities for aromatics were increased from 5.3 % to 52.3 % over [Ga]ZSM-5 and from 10.1% to 25.7% over [Al]ZSM-5. NH₃ TPD of [Ga]ZSM-5 indicated that the sites of medium acidity play an important role in the formation of aromatics. When H₂ and CO were added to the reactant of pentane, the production of methane and ethane increased and that of aromatics decreased.     

An In Situ ESR Study of Pd/H-ZSM-5 Interaction with Different Adsorbents

In situ ESR at 120–473 K permits to monitor formation of transient paramagnetic ions/complexes (isolated Pd⁺ sites; Pd⁺/H₂O; Pd⁺/C₆H₆) upon interaction of isolated Pd²⁺ cations stabilized by the H-ZSM-5 matrix with different organic compounds and gas mixtures (NO, O₂, H₂O, H₂, propene, benzene). The in situ study provides insight into the elementary steps of redox processes on isolated Pd species in H-ZSM-5 zeolite under realistic conditions. Adsorbed water stabilizes the transient paramagnetic complex and decreases the rate of Pd²⁺ to Pd⁰ reduction by H₂. Strong bonding of NO _x ligands to Pd²⁺ species suppresses the reduction of Pd(II) ions. Sorption of benzene on preoxidized Pd²⁺/HZSM-5 is accompanied by an easy formation of organic cation-radicals and of a Pd⁺/benzene complex, the paramagnetic Pd⁺/benzene structure indicating a surprisingly high resistance to further reduction to Pd⁰. Illumination of the Pd/HZSM-5 by UV-visible light causes no measurable change in the redox properties of the catalyst.     

An efficient method for a numerical description of virgin olive oil color with only two absorbance measurements

Four polynomial expressions are obtained that provide a good approximation and an easy, rapid calculation of the chromatic coordinates and the chroma—L ^*, a ^*, b ^*, and C—for the illuminant C and the standard observer, for a virgin or extra virgin olive oil; absorbance is measured at only 480 and 670 nm. These are as follows: L ^*=0.556458(A₄₈₀)²−2.51145A₄₈₀+0.55504(A₆₇₀)²−8.53016A₆₇₀+98.4089; a ^*=0.177372(A₄₈₀)²+2.1363A₄₈₀+1.43254(A₆₇₀)²−0.789231A₆₇₀−13.9246; b ^*=−16.0277(A₄₈₀)²+79.8932A₄₈₀−5.06558(A₆₇₀)²+3.36169A₆₇₀+31.9405; C=−15.8439(A₄₈₀)²+78.9312A₄₈₀−5.26784(A₆₇₀)²+3.56917A₆₇₀+33.3927. These give acceptable results, making the method a practical alternative to the extremely laborious Commission Internationale d’Eclairage (CIE) L ^* a ^* b ^* system, by which 391 absorbance values must be measured individually, nanometer by nanometer, before applying more complex equations. The validity of the proposed method has been confirmed by comparison, using a set of 20 sample oils different from the set of 25 oils used to generate the order of the equations. The variations between the values provided by the proposed and standard methods, respectively, had a mean of 0.00 for each of the chromatic variables—L ^* , a ^* , b ^* , and C; SD were moderate (0.71, 0.52, 1.22, and 1.22, respectively); the root mean square and the R ²-terms also confirmed the validity of the method.     

NanoZnO initiated polymerization of N-vinylcarbazole (NVC) and evaluation of a poly(N-vinylcarbazole)–ZnO nanocomposite

The polymerization of N-vinylcarbazole was conducted in bulk in presence of ZnO without any external initiator and a nanocomposite of poly(N-vinylcarbazole)–ZnO (PNVC–ZnO) was isolated from the system. The polymerization of N-vinylcarbazole by ZnO impregnated with acetylene black (AB) and Fe³⁺ was also conducted to isolate the respective AB and Fe³⁺ loaded PNVC–ZnO composites, PNVC–ZnO(AB) and PNVC–ZnO(Fe³⁺). The formation of the poly(N-vinylcarbazole) in these systems was confirmed by FTIR, UV–vis and emission spectroscopic analysis. TGA, DSC and SEM characteristics of these composites were evaluated in details. XRD analysis revealed no crystanillity in poly(N-vinylcarbazole) moiety. PNVC–ZnO was nonconducting but PNVC–ZnO(AB) and PNVC–ZnO(Fe³⁺) systems exhibited conductivities in the range 0.12 and 10⁻³ S/cm respectively. A carbocationic propagation pathway was suggested to explain the initiation of N-vinylcarbazole by Zn⁺⁺ moiety in ZnO. Kinetic studies revealed that the polymerization is first order with respect to ZnO and the monomer concentration respectively.     

Reversible collapse and Mg release of de- and rehydroxylated homoionic cis-vacant montmorillonites

Homoionic Na⁺, Ca²⁺, Sr²⁺, Li⁺, Cu²⁺ and Zn²⁺ samples of the <2 μm fraction of a cis-vacant montmorillonite from Linden (Bavaria) were steam treated at 200°C (≈1.5 MPa), 240°C (≈3.3 MPa) and 300°C (≈8.0 MPa) after dehydroxylation at temperatures up to 630°C. Cation exchange capacity (CEC) measurements, determination of exchangeable cations and X-ray diffraction (XRD), supplemented by thermoanalytical investigations of the evolved water in a thermobalance linked to a mass spectrometer, infrared (IR) and electron spin resonance (ESR) spectroscopy were employed to obtain information about the state of expandability and structural changes of swellable montmorillonite and the sites of interlayer and octahedral cations after heating and rehydroxylation.The XRD pattern of the initial samples showed a well-defined (001) reflection according to the interlayer cation and its hydration state under laboratory atmosphere. After dehydroxylation the pattern exhibited (001) reflections between 9.6 and 9.8 Å, corresponding to a collapsed structure for all samples. The Na⁺-, Ca²⁺- and Sr²⁺-rich montmorillonites regained partial expandability after rehydroxylation at 200°C and full expandability after rehydroxylation at 300°C if the dehydroxylation temperature was less than 630°C. Rehydroxylation at 300°C of the Cu²⁺- and Zn²⁺-rich montmorillonites did not cause reexpansion, whereas the Li⁺-rich samples recovered a partial swellability after rehydroxylation at 240°C and nearly the full swellability after rehydroxylation at 300°C.The Li⁺-, Cu²⁺- and Zn²⁺-rich samples underwent a strong CEC reduction due to migration of the interlayer cations into the 2:1 layer before dehydroxylation started. After rehydroxylation under water steam Cu²⁺- and Zn²⁺-rich samples released 16–30 meq/100 g of Mg²⁺ from the structure, increasing with the steam temperature. Mg²⁺ release was not observed for the Li⁺-rich montmorillonite.     

Synthesis of hollandite-type LixMnO2 by Li ion-exchange in molten salt and lithium insertion characteristics

The Li⁺ ion-exchange reaction of K⁺-type α-K_0.14MnO_1.93·nH₂O containing different amounts of water molecules (n = 0-0.15) with a large (2 × 2) tunnel structure has been investigated in a LiNO₃-LiCl molten salt at 300 °C. The Li⁺ ion-exchanged products were examined by chemical analysis, X-ray diffraction, and transmission electron microscopy measurements. The K⁺ ions and the hydrogens of the water molecules in the (2 × 2) tunnels of α-MnO₂ were exchanged by Li⁺ ions in the molten salt, resulting in the Li⁺-type α-MnO₂ containing different amounts of Li⁺ ions and lithium oxide (Li₂O) in the (2 × 2) tunnels with maintaining the original hollandite structure.The electrochemical properties and structural variation with initial discharge and charge-discharge cycling of the Li⁺ ion-exchanged α-MnO₂ samples have been investigated as insertion compounds in the search for new cathode materials for rechargeable lithium batteries. The Li⁺ ion-exchanged α-MnO₂ samples provided higher capacities and higher Li⁺ ion diffusivity than the parent K⁺-type materials on initial discharge and charge-discharge cyclings, probably due to the structural stabilization with the existence of Li₂O in the (2 × 2) tunnels.     

Effect of Coordination Modes of HL Ligand on the Molecular Architecture of Its Transition Metal Complexes (HL = 5-Methyl-2-Phenyl-4-[(2-<Emphasis Type="Italic">o</Emphasis>-Tolylamino)-Phenylmethylene]pyrazol-3(2H)-one)

Abstract  Two Ag⁺ complexes [Ag(HL)₂(PF₆)] (1) and [(AgL) _n  · n(CH₂Cl₂) · n(0.5H₂O)] (2) (HL = 5-methyl-2-phenyl-4-[(2-o-tolylamino)-phenylmethylene]pyrazol-3(2H)-one) were synthesized and structurally characterized by EA analysis, IR spectra and X-ray crystallography. The result shows that two expected coordination modes (Modes I and III in Scheme 1) of the HL ligand, can be observed in its Ag⁺ complexes, while not in other transition metal ions (Ni²⁺, Co²⁺ or Cu²⁺) complexes whether deprotonation or not for the HL ligand. Graphical Abstract  Three possible coordination modes (Modes I, II or III in Scheme 1) of the selected HL (HL = 5-methyl-2-phenyl-4-[(2-o-tolylamino)-phenylmethylene]pyrazol-3(2H)-one) ligand, can be adopted, in which Modes I and III can be observed in its two Ag⁺ complexes [Ag(HL)₂(PF₆)](1) and [(AgL) _n  · n(CH₂Cl₂) · n(0.5H₂O)] (2), while Mode II just observed in its transition metal ions (Cu²⁺, Ni²⁺, or Co²⁺) complexes, resulting from the deprotonatd form of the HL ligand and the coordination characters of transition metal ions.      

Effects of Na Addition, Pyridine Preadsorption, and Water Preadsorption on the Hydrogen Adsorption Property of Pt/SO4 2--ZrO2

Hydrogen adsorption was studied for Pt/SO₄ ^2--ZrO₂ samples modified with Na addition, pyridine preadsorption, and water preadsorption to elucidate the relation between the rate and capacity of hydrogen adsorption and the surface state. The surface states were monitored by XRD, IR, ammonia TPD, and measurement of catalytic activity for cyclohexane isomerization. All the modifications suppressed the hydrogen uptake. It was suggested that Lewis acid sites promote the hydrogen uptake by stabilizing spiltover hydrogen atoms.     

Purification and properties of lipase from the anaerobepropionibacterium acidi-propionici

A lipase secreted by the anaerobePropionibacterium acidipropionici was purified 52-fold with 27% recovery by employing a three-step purification protocol. The enzyme has a small molecular mass (Mr = 6000–8000) as determined by gel filtration and ultracentrifugation. It hydrolyzed palm oil, coconut oil, castor oil, olive oil, groundnut oil and tributyrin. Enzyme activity was inhibited by Ni²⁺, Ba²⁺, Mg²⁺, Cu²⁺, ethylenediaminetetraacetic acid, iodoacetamide, N-acetylimidazole and nonidet P-40 but stimulated by Ca²⁺, Co²⁺, K⁺, Fe²⁺, sodium dodecyl sulfate and N-bromosuccinamide. The enzyme showed substrate inhibition for both tributyrin andp-nitrophenyl acetate.     

Temperature programmed desorption of <Emphasis Type="Italic">n</Emphasis>-hexane and <Emphasis Type="Italic">n</Emphasis>-heptane from MFI and FAU zeolites

TPD studies of n-hexane and n-heptane from NaX, Y and ZSM-5 (Na⁺ or H⁺ exchanged) in the experimental system with a TCD detector were performed, using pure He or He/n-alkane mixture as a carrier gas. The TPD profiles with one desorption peak for Y and two peaks for ZSM-5, measured using He/hydrocarbon mixture, were similar to the previously reported equilibrated thermodesorption results. TPD profiles were accurately fitted with a model based on the equilibrium control of the desorption and the adsorption functions derived from the Langmuir or dual site Langmuir isotherms.     

A new rhodamine-based single molecule multianalyte (Cu, Hg) sensor and its application in the biological system

A new single molecule multianalyte sensor, vanillic aldehyde rhodamine 6G hydrazone has been designed for the selective detection of Cu²⁺ and Hg²⁺ ions. UV/Vis spectroscopy indicates that the sensor is a good chromogenic chemosensor for Cu²⁺ in 1:99 (v/v) ethanol-water media. Whereas, other ions, such as Li⁺, Na⁺, Mg²⁺, K⁺, Ca²⁺, Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Zn²⁺, Ag⁺, Cd²⁺, Ba²⁺, Hg²⁺ and Pb²⁺ failed to generate a distinct response. Fluorescence spectral data reveals that the sensor is an excellent fluorescent chemosensor for Hg²⁺ in aqueous ethanol solution and with no fluorescent response toward other ions. The spectroscopic behavior of the sensor in living cells indicated that it can be used for the detection of Cu²⁺ and Hg²⁺ in environmental and biological systems. Mechanisms for the high selectivity of the sensor to Cu²⁺ and Hg²⁺ are discussed.     

Solvent Extraction of Li+ using Organophosphorus Ligands in the Presence of Ammonia

In this work, the selective extraction of Li⁺ with the aid of organophosphorus ligands (H-OP) including phenylphosphonic (H-PHO), phenylphosphinic (H-PHI) and bis(2-ethylhexyl) phosphoric (H-BIS) acids in the absence and presence of ammonia was studied. Adding NH₃ to the aqueous phase resulted in significant improvement in the % extraction of Li⁺ into the organic phase containing H-OP ligands. The highest % extraction values obtained in the case of H-PHO, H-PHI, and H-BIS were 43.2%, 45.7%, and 90.0%, respectively. Two mechanisms were inferred; the first was that the extraction equilibrium reaction of LiCl + H-OP ? Li-OP + HCl shifted forward due the reaction of the produced HCl with NH₃. The second mechanism was that the Li⁺/NH₄⁺ exchange of NH₄-OP (produced from the reaction of H-OP with NH₃) was easier than Li⁺/H⁺ exchange of H-OP itself. Competitive extraction experiments indicated that the selectivity factors of Li⁺ over Na⁺ and K⁺ were strongly dependent on the concentration of H-OP ligands which suggested that aggregation of ligand molecules via hydrogen bonding is the limiting factor for selectivity.     

Mediation of cardiac glycoside insensitivity in the monarch butterfly (Danaus plexippus): Role of an amino acid substitution in the ouabain binding site of Na+,K+-ATPase

The Monarch butterfly (Danaus plexippus) sequesters cardiac glycosides (CG) for its chemical defense against predators. Larvae and adults of this butterfly are insensitive towards dietary cardiac glycosides, whereas other Lepidoptera are sensitive and intoxicated by ouabain. Ouabain inhibits Na⁺,K⁺-ATPase by binding to its -subunit. We have amplified and cloned the DNA-sequence encoding the respective ouabain binding site. Instead of the amino acid asparagine at position 122 in ouabain-sensitive insects, the Monarch has a histidine in the putative ouabain binding site, which consists of 12 amino acids. Starting with the CG-sensitive Na⁺,K⁺-ATPase gene fromDrosophila, we converted pos. 122 to a histidine residue as inDanaus plexippus by site-directed mutagenesis. Human embryonic kidney cells (HEK) (which are sensitive to ouabain) were transfected with the mutated Na⁺,K⁺-ATPase gene in a pSVDF-expression vector and showed a transient expression of the mutatedDrosophila Na⁺,K⁺-ATPase. When treated with ouabain, the transfected cells tolerated ouabain at a concentration of 50 mM, whereas untransformed controls or controls transfected with the unmutatedDrosophila gene, showed a substantial mortality. This result implies that the asparagine to histidine exchange contributes to ouabain insensitivity in the Monarch. In two other CG-sequestering insects, e.g.,Danaus gilippus andSyntomeida epilais, the pattern of amino acid substitution differed, indicating that the Monarch has acquired this mutation independently during evolution.     

Selective Catalytic Reduction of NOx over H-ZSM-5 Under Lean Conditions Using Transient NH3 Supply

The selective catalytic reduction (SCR) of NO _x over zeolite H-ZSM-5 with ammonia was investigated using in situ FTIR spectroscopy and flow reactor measurements. The adsorption of ammonia and the reaction between NO _x , O₂ and either pre-adsorbed ammonia or transiently supplied ammonia were investigated for either NO or equimolar amounts of NO and NO₂. With transient ammonia supply the total NO reduction increased and the selectivity to N₂O formation decreased compared to continuous supply. The FTIR experiments revealed that NO _x reacts with ammonia adsorbed on Brønsted acid sites as NH₄ ⁺ ions. These experiments further indicated that adsorbed -NO₂ ^– is formed during the SCR reaction over H-ZSM-5.     

Studies on promising cell performance with H2SO4 as the catholyte for electrogeneration of Ag2+ from Ag+ in HNO3 anolyte in mediated electrochemical oxidation process

Electrochemical performance of a divided cell with electrogeneration of Ag²⁺ from Ag⁺ in 6 M HNO₃ anolyte has been studied with 6 M HNO₃ or 3 M H₂SO₄ as the catholyte. This work arose because in mediated electrochemical oxidation (MEO) processes with Ag(II)/Ag(I) redox mediator, HNO₃ is generally used as catholyte, which, however, produces NO _x gases in the cathode compartment. The performance of the cell with 6 M HNO₃ or 3 M H₂SO₄ as the catholyte has been compared in terms of (i) the acid concentration in the cathode compartment, (ii) the Ag⁺ to Ag²⁺ conversion efficiency in the anolyte, (iii) the migration of Ag⁺ from anolyte to catholyte across the membrane separator, and (iv) the cell voltage. Studies with various concentrations of H₂SO₄ catholyte have been carried-out, and the cathode surfaces have been analyzed by SEM and EDXA; similarly, the precipitated material collected in the cathode compartment at higher H₂SO₄ concentrations has been analyzed by XRD to understand the underlying processes. The various beneficial effects in using H₂SO₄ as catholyte have been presented. A simple cathode surface renewal method relatively free from Ag deposit has been suggested.     

Thermal and chemical stability of Cu–Zn–Cr-LDHs prepared by accelerated carbonation

Layered double hydroxides Cu_xZn_6 − xCr₂(OH)₁₆(CO₃)·4H₂O with different molar ratios of Cu/Zn/Cr were synthesized by accelerated carbonation. The products were characterized by XRD, SEM, FT-IR and TG-DTG-DSC-MS. The chemical stability was tested by the modified Toxicity Characteristic Leaching Procedure (TCLP). The results showed that the products were the mixture of Cu_xZn_6 − xCr₂(OH)₁₆(CO₃)·4H₂O and (CuZn)₂(CO₃)(OH)₂, with similar thermal behavior. All products were chemically stable with reduced leaching at pH > 6 (Cu²⁺, Zn²⁺) or > 5 (Cr³⁺).