A hemidirected 1-D coordination polymer [Pb2(H2O)2(HBTC)2] · 3H2O extended in holodirected 3-D by weak Pb–O interactions

A new complex, [Pb₂(H₂O)₂(HBTC)₂] · 3H₂O (H₃BTC = 1,3,5-Benzenetricarboxylic acid) (1), has been synthesized under hydrothermal condition. The single-crystal analysis shows that 1 consists of 1-D double-chains with Pb(II) six-coordinated by three H₃BTC and one H₂O molecule with the Pb–O bond distances in the range of 2.56–2.76 Å. When the Pb–O bonding limit extends from 2.76 to 2.90 Å, the potential weak bonds of Pb–O can be found and the coordination number of Pb will increase from six to nine. As a result, the coordination geometry of Pb(II) transforms from hemidirected to holodirected and an infinite 3-D framework is obtained by the connection of the double-chains. The IR spectrum and the TGA–DTA curve of 1 are also reported in this paper.     

H2O-tolerant monolithic catalysts for preferential oxidation of carbon monoxide in the presence of hydrogen

Pt–Fe/mordenite (4 wt% Pt–0.5 wt% Fe) powder catalysts were wash-coated onto ceramic straight-channel monoliths by using silica- and/or alumina-sol as a binder, and were evaluated for the preferential oxidation of carbon monoxide (PROX) in a hydrogen-rich gas. In a synthetic reformate gas (1% CO, 1% O₂, 5% H₂O, 20% CO₂, and balance H₂), the CO concentration was reduced to less than 20 ppm at temperatures ranging from 100 to 130 °C. After a certain period of the PROX reaction, condensation of H₂O in the pores of the mordenite-support occurred over the monolithic catalyst, which was wash-coated with alumina-sol, in the lower temperature range (100–120 °C), resulting in a rapid increase in CO concentration. The monolithic catalyst wash-coated with silica-sol, however, showed an excellent tolerance against H₂O condensation and offered a stable catalytic performance, maintaining a CO concentration of ca. 20 ppm for 200 h. The H₂O-tolerant characteristic was attributed to the relatively small adsorption amount of H₂O over the silica-modified monolithic catalyst.     

Exploration of molten hydroxide electrochemistry for thermal battery applications

The electrochemistry of molten LiOH–NaOH, LiOH–KOH, and NaOH–KOH was investigated using platinum, palladium, nickel, silver, aluminum and other electrodes. The fast kinetics of the Ag⁺/Ag electrode reaction suggests its use as a reference electrode in molten hydroxides. The key equilibrium reaction in each of these melts is 2 OH^– = H₂O + O^2– where H₂O is the Lux-Flood acid (oxide ion acceptor) and O^2– is the Lux–Flood base. This reaction dictates the minimum H₂O content attainable in the melt. Extensive heating at 500 °C simply converts more of the alkali metal hydroxide into the corresponding oxide, that is, Li₂O, Na₂O or K₂O. Thermodynamic calculations suggest that Li₂O acts as a Lux–Flood acid in molten NaOH–KOH via the dissolution reaction Li₂O_(s) + 2 OH^– = 2 LiO^– + H₂O whereas Na₂O acts as a Lux–Flood base, Na₂O_(s) = 2 Na⁺ + O^2–. The dominant limiting anodic reaction on platinum in all three melts is the oxidation of OH^– to yield oxygen, that is 2 OH^– 1/2 O₂ + H₂O + 2 e^–. The limiting cathodic reaction in these melts is the reduction of water in acidic melts ([H₂O] [O^2–]) and the reduction of Na⁺ or K⁺ in basic melts. The direct reduction of OH^– to hydrogen and O^2– is thermodynamically impossible in molten hydroxides. The electrostability window for thermal battery applications in molten hydroxides at 250–300 °C is 1.5 V in acidic melts and 2.5 V in basic melts. The use of aluminum substrates could possibly extend this window to 3 V or higher. Preliminary tests of the Li–Fe (LAN) anode in molten LiOH–KOH and NaOH–KOH show that this anode is not stable in these melts at acidic conditions. The presence of superoxide ions in these acidic melts likely contributes to this instability of lithium anodes. Thermal battery development using molten hydroxides will likely require less active anode materials such as Li–Al alloys or the use of more basic melts. It is well established that sodium metal is both soluble and stable in basic NaOH–KOH melts and has been used as a reference electrode for this system.     

The high dispersion of CuCl2 in NaZSM-5 by using microwave technique

By using microwave technique, the high dispersion of CuCl₂ in NaZSM-5 zeolite (CuCl₂·2H₂O/NaZSM-5 ratio of 0–0.50 g/g) has been prepared. The mechanical mixture of CuCl₂-2H₂O and NaZSM-5 (CuCl₂·2H₂O/NaZSM-5 ratio of 0–0.50 g/g) shows characteristic XRD peaks of both NaZSM-5 and crystalline CuCl₂·2H₂O. Notably, after reaction of the above samples in a microwave oven for 10 min, the sample XRD patterns only exhibit the peaks assigned to NaZSM-5, while the peaks assigned to crystalline CuCl₂·2H₂O disappear completely, indicating that CuCl₂·2H₂O no longer exists in the crystalline state in the CuCl₂·2H₂O/NaZSM-5 samples. Additionally, in DTA curves, we cannot observe the melting point of CuCl₂ in a CuCl₂·2H₂O/NaZSM-5 sample (CuCl₂·2H₂O/NaZSM-5 ratio of 0–0.5 g/g) treated in a microwave oven, indicating that there is no CuCl₂ crystalline phase in the CuCl₂·2H₂O/NaZSM-5 samples (CuCl₂·2H₂O/NaZSM-5 ratio of 0–0.50 g/g).     

Selective oxidation of CO in the presence of H2, CO2 and H2O, on different zeolite-supported Pt catalysts

The selective oxidation of CO in the presence of H₂O and CO₂ has been studied on Pt supported on different zeolitic materials (MOR, ZSM-5, FAU and ETS-10) using a range of operating conditions and a variety of characterization techniques. The behavior of the Pt–ETS-10 and Pt–FAU catalysts has been investigated in more depth and the results obtained have been compared and related to the different characteristics of the supports. The best results in the presence of H₂O and CO₂ were obtained with Pt–FAU catalysts, showing stable catalytic activity and complete conversion of CO (λ = 2) at 439 K.     

On the Glass Formation in the Na2O–SiO2–H2O System

The glass formation in the Na₂O–SiO₂–H₂O system is considered in the framework of the free volume theory of glasses. The boundaries of the glass transition range in the given system are determined from the dependences of the specific volume and the degree of connectivity on the water content in the system. The differences in the structure of hydrated glasses prepared by different methods are revealed. It is demonstrated that the molecular packing coefficients of the structures formed by drying of sodium silicate solutions are smaller than those of glasses prepared by hydration of anhydrous glasses. The densities are determined and the molar volumes are calculated for hydrated glasses in the Na₂O–SiO₂–H₂O system with a water content of 12–23 wt % (33–51 mol %) at a constant molar ratio SiO₂ : Na₂O = 2.8. The correlation relationship for the partial molar volume of water as a component of hydrated glasses is proposed as a function of the water content in the system. The use of this dependence allows one to calculate the molar volumes (densities) of hydrated glasses with different water contents.     

A peculiar heterotrimetallic Mn–Co–Ni complex: Synthesis, crystal structure and magnetic properties

The first complex [Mn(H₂O)₆][NiCo(TTHA)(H₂O)₂] · 4H₂O 1 (TTHA⁶⁻ = triethylenetetraminehexaacetate) containing Mn^II–Co^II–Ni^II three different 3d metal ions is synthesized and magnetic measurement suggests that ferromagnetic interactions occur between Ni²⁺ ions and rarely found low-spin Co²⁺ ions.     

Electrochemical characteristics and structural changes of molybdenum trioxide hydrates as cathode materials for lithium batteries

Several characteristics of MoO₃·2H₂O and MoO₃·H₂O, such as thermal behaviour and conductivity and the electrochemical behaviour and structural changes associated with discharge and charge have been investigated. The suitability of these substances as new cathode materials for non-aqueous lithium batteries has been assessed. MoO₃·H₂O, having only one coordinated water molecule, showed a discharge capacity of about 400 Ah kg^–1 of acid weight and a discharge potential around 2.5 V vs Li/Li⁺. This capacity was much higher than the 280 Ah kg^–1 of anhydrous MoO₃.MoO₃·H₂O showed good charge-discharge cyclic behaviour at a capacity below l e^–/Mo while keeping the original layered lattice on cycling. In addition, the crystal system of MoO₃·H₂O was found to be changed from a monoclinic system to orthorhombic with lattice parameters ofa=0.5285 nm,b=1.0824 nm,c=0.5237 nm on discharge to 0.5 e^–/Mo.This paper was originally presented at the Fall 1987 Meeting of the Electrochemical Society, Inc. held at Honolulu, Hawaii (Proceedings of the Symposium on Primary and Secondary Ambient Temperature Batteries, PV88-6, p. 484–493 (1987).     

Electrochemical lean-deNOx catalyst using H-conducting solid polymer electrolyte

The reduction of NO to N₂/N₂O in the presence of excess O₂ has been successfully achieved at 70 °C using an electrochemical cell of the type, 0.1% NO, 0–10% O₂, Pt | NAFION | Pt, H₂O. An H⁺-conducting solid polymer electrolyte (SPE) plays a key role in evolving hydrogen on the Pt cathode, where the catalytic NO–H₂ takes place. It was revealed that the competitive H₂–O₂ reaction is suppressed because the Pt surface was covered with stable nitrate (NO₃) species, which blocks oxygen adsorption hereon. The inhibition of H₂–O₂ reaction becomes most efficient at 100 °C in agreement with the optimal operation temperature range of SPE. The reduction efficiency of NO in an excess O₂ could be improved by packing 1 wt% Pt/ZSM-5 catalyst in the cathode room. The combination between the SPE cell and Pt catalysts can broadly be applied to novel low-temperature deNO_x processes in a strongly oxidizing atmosphere.     

State Parameters and Phase Transformations in Carbonized Periclase Refractories

The effect of temperature and formulation (relative volumes of the gas phase) on phase and chemical transformations in the MgO – C – H₂O – air system at 298 – 2400 K is considered using methods of thermodynamic and physicochemical simulation with a view to using carbonized periclase refractories under industrial conditions. Temperature ranges for stable existence of refractory phases and formulation ranges (for the gas phase) with allowance for different chemical homo- and heterophase interactions are determined. Effects of temperature, concentration, and pressure of pore gases (CO₂, CO, CH₄, H₂O, H₂, etc.) on the bulk material and effects of the carbon component, porosity, intrinsic and atmospheric moisture on gasification processes are considered in terms of a theoretical simulation model.     

Electrodeposition of catalytically active Co-Ni-Tl alloy powders from dilute sulphate baths

Cobalt-nickel-thallium alloy powders were electrodeposited from dilute metal sulphate baths of composition: 0.007–0.0245 mol l^–1 CoSO₄·7H₂O, 0.0245–0.007 mol l^–1 NiSO₄·6H₂O, 0.001 mol l^–1 TlCl, 0.5 mol l^–1 (NH₄)₂SO₄, 0.07 mol l^–1 Na₂SO₄·10H₂O and 0.4 mol l^–1 H₃BO₃. The cathodic polarization curves were traced during electrodeposition and utilized in the discussion of a reaction mechanism for the electrolytic powder deposition. The alloy composition and the cathodic current efficiency were influenced to a great extent by the bath composition (I) and slightly by the deposition current density (II). Irrespective of variables (I) and (II), the electrodeposition of the alloy belonged to the anomalous type. The surface morphology and the catalytic activity, towards the decomposition of 0.4% H₂O₂ solution, of the as-deposited alloy powders were affected predominantly by the percentage of cobalt in the alloy. X-ray diffraction studies showed that the alloys consisted mainly of the face-centred cubic nickel phase either alone or with minor proportions of face-centred cubic cobalt phase and hexagonal close-packed -cobalt phase. The occurrence of the latter phases was observed only in the alloys with a higher cobalt percentage than nickel.     

High temperature SrCe0.9Eu0.1O3−δ proton conducting membrane reactor for H2 production using the water–gas shift reaction

The water–gas shift (WGS) reaction is used to shift the CO/H₂ ratio prior to Fischer–Tropsch synthesis and/or to increase H₂ yield. A WGS membrane reactor was developed using a mixed protonic–electronic conducting SrCe_0.9Eu_0.1O_3−δ membrane coated on a Ni–SrCeO_3−δ support. The membrane reactor overcomes the thermodynamic equilibrium limitations. A 46% increase in CO conversion and total H₂ yield was achieved at 900 °C under 3% CO and 6% H₂O, resulting in a 92% single pass H₂ production yield and 32% single pass yield of pure permeated H₂.     

Hydrogen permeance and the effect of H2O and CO on the permeability of Pd0.75Ag0.25 membranes under gas-driven permeation and plasma-driven permeation

The hydrogen permeance of Pd_0.75Ag_0.25 membranes was measured in the presence of pure H₂ or mixtures of H₂ with CO and H₂O at temperatures in the range of 300–773 K and at atmospheric pressure under gas-driven permeation (GDP) and plasma-driven permeation (PDP). The Arrhenius plots of the permeability through these membranes versus the inverse temperature showed a small peak in the intermediate temperature range and different activation energies in the low and high temperature ranges. The experimental data also indicated a more pronounced effect of CO on the permeability than H₂O, and a similar effect of GDP and PDP. The stronger inhibition by CO was due to the strong interaction between CO and Pd, and this effect was eliminated at temperatures higher than 623 K.     

Estimation of the Combustion and Detonation Parameters for Hydrocarbon Gas Hydrates

Calculated combustion and detonation parameters for methane—oxygen (air)—H₂O and acetylene—oxygen (air)—H₂O mixtures are presented. The values of the critical detonation–initiation energy are estimated as applied to methane and acetylene hydrates.     

Preparation of a pigment in the Cr(III)-Co(II)-NO3-H2O system

Joint precipitation of Cr(III) and Co(II) ions at pH = 1.8–12.0 and 2.5–12.0 is investigated. It is established that a Cr₂Co₃O₆ · 10H₂O hydrocomplex precipitates in the Cr(III)-Co(II) -NO₃- H₂O system at pH = 3.0 –10.5 and is dehydrated at 940°C. The compound obtained can be used as a pigment for preparing overglaze paints and color glazes for decorating porcelain, faience, and majolica articles.Translated from Steklo i Keramika, No. 10, pp. 23–24, October, 1995.     

Single- and double-stage catalytic preferential CO oxidation in H2-rich stream over an α-Fe2O3-promoted CuO–CeO2 catalyst

Single- and double-stage catalytic preferential CO oxidation (CO-PrOx) over-Fe₂O₃-promoted CuO–CeO₂ in a H₂-rich stream has been investigated in this work. The catalyst was prepared by the urea-nitrate combustion method and was characterized by X-ray diffractometer (XRD), X-ray fluorescence (XRF), Brunauer–Emmet–Teller (BET), transmission electron microscope (TEM), and scanning electron microscope (SEM). The catalytic activity tests were carried out in the temperature range of 50–225 °C under atmospheric pressure. The results of the single-stage reaction indicated that complete CO oxidation was obtained when operating at a O₂/CO ratio of 1.5, W/F ratio of 0.36 g s/cm³, and at a reaction temperature of 175 °C. At these conditions, H₂ consumption in the oxidation was estimated at 58.4%. Applying the same conditions to the double-stage reaction, complete CO oxidation was found and H₂ consumption in the oxidation was reduced about 4.9%. When decreasing the double-stage reaction temperature to 150 °C, the results elucidated that CO could be converted to CO₂ completely while H₂ consumption in the oxidation was further reduced to 33.5%. A temperature blocking 2² factorial design has been used to describe the importance of the factors influencing the catalytic activity. The factorial design was according to the experimental results. When adding CO₂ and H₂O in feed, reduction of CO conversion for single- and double-stage reaction is obtained due to a blocking of CO₂ and H₂O at a catalytic active site. Comparing CO conversion obtained when operating with/without CO₂ and H₂O in feed for single- and double-stage reaction, less reduction is achieved when operating in double-stage reaction.     

Solvothermal synthesis of 1D and 2D cobalt(II) and nickel(II) coordination polymers with 2,5-dihydroxy-p-benzenediacetic acid

1D cobalt(II) and nickel(II) coordination polymers {[Co(dba)(H₂O)₄] · H₂O}_n (1) and {[Ni(dba)(H₂O)₄] · H₂O}_n (2) (H₂dba = 2,5-dihydroxy-p-benzenediacetic acid) were synthesized under low temperature solvothermal condition. When 4,4′-bipyridine (bpy) was introduced to the synthetic systems of 1 and 2, respectively, two novel 2D coordination polymers {[Co(dba)(bpy)] · 0.5H₂O}_n (3) and [Ni(dba)(bpy)(H₂O)₂]_n (4) with different structures were obtained. All of the compounds were characterized by elemental analysis, FT-IR, UV–Vis spectra and single crystal X-ray diffraction.     

Synthesis, crystal structures and photoluminescence of Zn–Ln heterometallic polymers based on pyridine-2,3-dicarboxylic acid

Three new two-dimensional 3d–4f isostructural heterometallic coordination polymers, namely [Ln₂Zn(2,3-pydc)₄(H₂O)₄·4H₂O]_n (Ln = Sm (1), Eu (2), Gd (3), 2,3-pydcH₂ = pyridine-2,3-dicarboxylic acid) have been successfully synthesized by the hydrothermal reactions of Ln₂O₃, Zn(NO₃)₂·6H₂O, H₂pydc and H₂O. X-ray diffraction analyses reveal that they possess a 2D heterometallic framework containing 1D lanthanide chains based on dimeric [Ln(2,3-pydc)₂(H₂O)₂]₂ unit. The Zn(II) ion, which is six-coordinated by four oxygen and two nitrogen atoms from four 2,3-pydc²⁻ ligands, as a bridge, links the lanthanide chains to make the 1D chains further extend into 2D layer framework. Furthermore, the neighboring layers are assembled into three-dimensional supramolecular network through inter-layer O–HO and C–HO hydrogen-bond interactions. In addition, the solid-state luminescent property of complex 2 was investigated.     

Synthesis and properties of a zeolite LEV analogue from the system—Na2O–Al2O3–SiO2–N,N-dimethylpiperidine chloride–H2O

A new structure-directing agent (SDA) was firstly reported for the synthesis of a zeolite LEV analogue. N,N-dimethyl piperidine performed the SDA function, and induced the synthesis of products from a zeolite MOR with 12-ring channels to a zeolite LEV analogue with only 8-ring channels. The zeolite LEV analogue was synthesized from gels with initial compositions (5.0–6.0)Na₂O–Al₂O₃–(10–200)SiO₂–(4.0–8.0)N,N-dimethyl piperidine–400H₂O at 150 °C. The ²⁹Si NMR spectra showed that the relative intensities of the first line at −115 ppm for low Si/Al ratios were lower than that at high Si/Al ratios. Varying ion exchanges led to different acidities in the zeolite LEV analogue, with the acidity of H-LEV-HCl higher than that of H-LEV-NH₃·H₂O. Zeolite H-LEV in hydration of propene showed a higher selectivity of 1-propanol.     

Preferential CO oxidation in H2-rich gas mixtures over Au/doped ceria catalysts

Nanosized gold catalysts supported on doped ceria were prepared by deposition–precipitation method. A deep characterization study by HRTEM/EDS, XRD, FT-Raman, TPR and FTIR was undergone in order to investigate the effect of ceria modification by various cations (Sm³⁺, La³⁺ and Zn²⁺) on structural and redox properties of gold catalysts. Doping of ceria affected in different way catalytic activity towards purification of H₂ via preferential CO oxidation. The following activity order was observed: Au/Zn–CeO₂ > Au/Sm–CeO₂ > Au/CeO₂ > Au/La–CeO₂. The differences in CO oxidation rates were ascribed to different concentration of metallic gold particles on the surface of Au catalysts (as confirmed by the intensity of the band at 2103 cm⁻¹ in the FTIR spectra collected during CO–O₂ interaction). Gold catalysts on modified ceria showed improved tolerance towards the presence of CO₂ and H₂O in the PROX feed. The spectroscopic experiments evidence enhanced reactivity when PROX is performed in the presence of H₂O already at 90 K.