Ethylene Epoxidation in Cylindrical Dielectric Barrier Discharge: Effects of Separate Ethylene/Oxygen Feed

The effects of separate C₂H₄/O₂ feed and C₂H₄ feed position on the ethylene epoxidation reaction in an AC cylindrical dielectric barrier discharge reactor were investigated. The highest EO selectivity of 34?% and EO yield of 7.5?%, as well as the lowest power consumption of 1.72?×?10^?16 Ws/molecule of EO produced, were obtained at a C₂H₄ feed position of 0.25, an O₂/C₂H₄ feed molar ratio of 1/4, an applied voltage of 13?kV, an input frequency of 550?Hz, and a total feed flow rate of 75?cm³/min. The results demonstrated, for the first time, that the separate feed of C₂H₄ and O₂ could provide better ethylene epoxidation performance in terms of higher EO selectivity and yield, and lower power consumption, as compared to the mixed feed. All undesired reactions including C₂H₄ cracking, dehydrogenation, oxidation, and coupling reactions are lowered by the ethylene separate feed because of a decrease in opportunity of ethylene molecules to be activated by generated electrons.     

Ethylene Epoxidation in Low-Temperature AC Dielectric Barrier Discharge: Effects of Oxygen-to-Ethylene Feed Molar Ratio and Operating Parameters

Ethylene oxide (EO), a valuable chemical feedstock in producing many industrial chemicals, which is industrially produced by the partial oxidation of ethylene, so-called ethylene epoxidation, has been of great interest in many global research studies. In this work, the epoxidation of ethylene under a low-temperature dielectric barrier discharge (DBD) was feasibly investigated to find the best operating conditions. It was experimentally found that the EO yield decreased with increasing O₂/C₂H₄ feed molar ratio, feed flow rate, input frequency, and electrode gap distance, while it increased with increasing applied voltage up to 19 kV. The highest EO yield of 5.6% was obtained when an input frequency of 500 Hz and an applied voltage of 19 kV were used, with an O₂/C₂H₄ feed molar ratio of 1:1, a feed flow rate of 50 cm³/min, and an electrode gap distance of 10 mm. Under these best conditions, the power consumption was found to be as low as 6.07 × 10⁻¹⁶ Ws/molecule of EO produced.     

Tailoring the Electronic Metal-Support Interactions in Supported Silver Catalysts through Al modification for Efficient Ethylene Epoxidation

Metal-modified catalysts have attracted extraordinary research attention in heterogeneous catalysis due to their enhanced geometric and electronic structures and outstanding catalytic performances. Silver (Ag) possesses necessary active sites for ethylene epoxidation, but the catalyst activity is usually sacrificed to obtain high selectivity towards ethylene oxide (EO). Herein, we report that using Al can help in tailoring the unoccupied 3d state of Ag on the MnO₂ support through strong electronic metal-support interactions (EMSIs), overcoming the activity-selectivity trade-off for ethylene epoxidation and resulting in a very high ethylene conversion rate (~100 %) with 90 % selectivity for EO under mild conditions (170 °C and atmospheric pressure). Structural characterization and theoretical calculations revealed that the EMSIs obtained by the Al modification tailor the unoccupied 3d state of Ag, modulating the adsorption of ethylene (C₂H₄) and oxygen (O₂) and facilitating EO desorption, resulting in high C₂H₄ conversion. Meanwhile, the increased number of positively charge Ag⁺ lowers the energy barrier for C₂H_4(ads) oxidation to produce oxametallacycle (OMC), inducing the unexpectedly high EO selectivity. Such an extraordinary electronic promotion provides new promising pathways for designing advanced metal catalysts with high activity and selectivity in selective oxidation reactions.     

Theoretical investigation on reaction pathways for ethylene epoxidation on Ti-decorated graphene

The activities of atomic Ti-decorated graphene (Ti/dG) for ethylene epoxidation and competitive paths for acetaldehyde (AA) formation are investigated by means of density functional theory together with the D3 dispersion correction (UM06-L-D3). Two reaction mechanisms for ethylene epoxidation, namely concerted and stepwise mechanisms, were considered. The computational results reveal that the electron transfer from graphene can effectively enhance the catalytic activity of Ti atom. Without graphene support, atomic Ti becomes an inert metal for this reaction. Strong adsorption and significant activation of the reactant O₂ molecule were observed on the Ti-decorated graphene material. Over the O₂-adsorbed Ti/dG, the direct attack of the olefin on an peroxo oxygen center is preferred. The activation for this step is 10.9 kcal mol^?1. After the reaction, an ethylene oxide is formed with one atomic oxygen on top of Ti. Consequently, a gaseous ethylene reacts with the remaining O atom of TiO moiety for the formation of the second ethylene oxide molecule. The formation of ethylene oxide over the TiO/dG involves a two-step process which is the formations of oxametallacycle intermediate and EO, respectively. The calculated barriers for these two steps are 9.9 and 18.9 kcal mol^?1, respectively. Furthermore, the Ti/dG showed a lower activation barrier toward EO formation than that of AA. Therefore, our theoretical study suggests that atomic Ti-decorated graphene could possess catalytic activity for ethylene epoxidation comparable to that of potential catalysts.     

Ethylene Epoxidation over Alumina- and Silica-Supported Silver Catalysts in Low-Temperature AC Dielectric Barrier Discharge

In this work, ethylene epoxidation reaction for ethylene oxide production over silver catalysts loaded on two different supports (silica and alumina particles) in a low-temperature AC dielectric barrier discharge (DBD) reactor was investigated. The DBD plasma system was operated under the following base conditions: an O₂/C₂H₄ feed molar ratio of 1/4, a total feed flow rate of 50 cm³/min, an electrode gap distance of 0.7 cm, an input frequency of 500 Hz, and an applied voltage of 19 kV. From the results, the presence of silver catalysts improved the ethylene oxide production performance. The silica support interestingly provided a higher ethylene oxide selectivity than the alumina support. The optimum Ag loading on the silica support was found to be 20 wt%, exhibiting the highest ethylene oxide selectivity of 30.6%.     

Epoxidation of cyclohexene with molecular oxygen by electrolysis combined with chemical catalysis

This paper describes an electrochemical coupling epoxidation of cyclohexene by molecular oxygen (O₂) under mild reaction conditions. Herein, the electroreduction of O₂ to hydrogen peroxide (H₂O₂) efficiently proceeds in a relatively environmentally friendly acetone/water medium containing electrolytes at 25–30 °C on a self-assembled H type of electrolysis cell with tree electrodes system, providing ca. 44.3 mM concentration of H₂O₂ under the optimal electrolysis conditions. The epoxidation of cyclohexene with in situ generated H₂O₂ simultaneously occurs upon catalysis by metal complexes, giving ca. 19.8 % of cyclohexene conversion with 78 % of epoxidative selectivity over the best catalyst 5-Cl-7-I-8-quinolinolato manganese(III) complex (Q₃Mn^III (e)). The present electrochemical coupling epoxidation result is nearly equivalent to the epoxidation of cyclohexene with adscititious H₂O₂ catalyzed by the Q₃Mn^III (e).     

Ethylene Epoxidation over Alumina-Supported Silver Catalysts in Low-Temperature AC Corona Discharge

In this paper, the epoxidation of ethylene over different catalysts—namely Ag/(low-surface-area, LSA)α-Al₂O₃, Ag/(high-surface-area, HSA)γ-Al₂O₃, and Au–Ag/(HSA)γ-Al₂O₃—in a low-temperature corona discharge system was investigated. In a comparison among the studied catalysts, the Ag/(LSA)α-Al₂O₃ catalyst was found to offer the highest selectivity for ethylene oxide, as well as the lowest selectivity for carbon dioxide and carbon monoxide. The selectivity for ethylene oxide increased with increasing applied voltage, while the selectivity for ethylene oxide remained unchanged when the frequency was varied in the range of 300–500 Hz. Nevertheless, the selectivity for ethylene oxide decreased with increasing frequency beyond 500 Hz. The optimum Ag loading on (LSA)α-Al₂O₃ was found to be 12.5 wt.%, at which a maximum ethylene oxide selectivity of 12.9% was obtained at the optimum applied voltage and input frequency of 15 kV and 500 Hz, respectively. Under these optimum conditions, the power consumption was found to be 12.6 × 10^?16 W s/molecule of ethylene oxide produced. In addition, a low oxygen-to-ethylene molar ratio and a low feed flow rate were also experimentally found to be beneficial for the ethylene epoxidation.     

Ethylene Epoxidation in Low-Temperature AC Dielectric Barrier Discharge: Effect of Electrode Geometry

In this work, the epoxidation of ethylene under a cylindrical dielectric barrier discharge (DBD) reactor and a parallel DBD reactor was comparatively studied. The effects of important operating parameters—feed O₂/C₂H₄ molar ratio, applied voltage, input frequency, and residence time—were investigated on the reaction performance in terms of reactant conversions, product selectivities, product yields, and power consumptions per molecule of ethylene converted and per molecule of ethylene oxide produced. The optimum conditions obtained from the operating parameter investigation were used for a comparative performance evaluation of both DBD reactor systems. It was found that under the optimum conditions of each system, the cylindrical DBD system exhibited superior epoxidation performance for ethylene oxide production compared to the parallel DBD system, indicating that the electrode geometry (electrode edge length-to-electrode surface area ratio) plays a significant role in the ethylene epoxidation.     

Preparation and electrochemical characterization of Ruddlesden–Popper oxide La4Ni3O10 cathode for IT-SOFCs by sol–gel method

La₄Ni₃O₁₀ oxide was synthesized as a cathode material for intermediate-temperature solid oxide fuel cells by a facile sol–gel method using a nonionic surfactant (EO)106(PO)70(EO)106 tri-block copolymer (F127) as the chelating agent. The crystal structure, electrical conductivity, and electrochemical properties of La₄Ni₃O₁₀ were investigated by X-ray diffraction, DC four-probe method, electrochemical impedance spectra, and I–V measurements. The La₄Ni₃O₁₀ cathode showed a significantly low polarization resistance (0.26 Ω cm²) and cathodic overpotential value (0.037 V at the current density of 0.1 A cm^?2) at 750 °C. The results measured suggest that the diffusion process was the rate-limiting step for the oxygen reduction reaction. The La₄Ni₃O₁₀ cathode revealed a high exchange current density value of 62.4 mA cm^?2 at 750 °C. Furthermore, an anode-supported single cell with La₄Ni₃O₁₀ cathode was fabricated and tested from 650 to 800 °C with humidified hydrogen (～3 vol% H₂O) as the fuel and the static air as the oxidant. The maximum power density of 900 mW cm^?2 was achieved at 750 °C.     

Flue Gas Desulfurization by Dielectric Barrier Discharge

There are many problems with flue gas desulfurization by traditional gas ionization discharge, including the large size of the plasma source, high energy consumption, and the need for a traditional desulfurization method. This paper introduces oxidization of SO₂ to sulfuric acid (H₂SO₄) in a duct by reactive oxygen species (O₂ ⁺, O₃) produced by strong ionization dielectric barrier discharge. The entire plasma reaction process is completed within the duct without the use of absorbents, catalysts, or large plasma source. The reactive oxygen species O₂ ⁺ reacts with gaseous H₂O in the flue gas to generate ·OH radicals, which can oxidize trace amounts of SO₂ in large volumes of the flue gas to produce H₂SO₄. Sulfuric acid is also produced by O₃ oxidation of SO₂ to SO₃, and SO₃ reacting with gaseous H₂O in the flue gas. Experimental results showed that with a gas temperature of 22 °C and reactive oxygen species injection rate of 0.84 mg/L, the SO₂ removal rate was 81.4 %, and the SO₄ ^2? concentration in the recovered liquid H₂SO₄ reached 53.8 g/L.     

Magnetic properties of nanocrystalline CuFe2O4 and kinetics of thermal decomposition of precursor

CuFe₂(C₂O₄)₃·4.5H₂O was synthesized by solid-state reaction at low heat using CuSO₄·5H₂O, FeSO₄·7H₂O, and Na₂C₂O₄ as raw materials. The spinel CuFe₂O₄ was obtained via calcining CuFe₂(C₂O₄)₃·4.5H₂O above 400 °C in air. The CuFe₂(C₂O₄)₃·4.5H₂O and its calcined products were characterized by thermogravimetry and differential scanning calorimetry, Fourier transform FT-IR, X-ray powder diffraction, scanning electron microscopy, energy dispersive X-ray spectrometer, and vibrating sample magnetometer. The result showed that CuFe₂O₄ obtained at 400 °C had a saturation magnetization of 33.5 emu g^?1. The thermal process of CuFe₂(C₂O₄)₃·4.5H₂O experienced three steps, which involved the dehydration of four and a half crystal water molecules at first, then decomposition of CuFe₂(C₂O₄)₃ into CuFe₂O₄ in air, and at last crystallization of CuFe₂O₄. Based on KAS equation, OFW equation, and their iterative equations, the values of the activation energy for the thermal process of CuFe₂(C₂O₄)₃·4.5H₂O were determined to be 85 ± 23 and 107 ± 7 kJ mol^?1 for the first and second thermal process steps, respectively. Dehydration of CuFe₂(C₂O₄)₃·4.5H₂O is multistep reaction mechanisms. Decomposition of CuFe₂(C₂O₄)₃ into CuFe₂O₄ could be simple reaction mechanism, probable mechanism function integral form of thermal decomposition of CuFe₂(C₂O₄)₃ is determined to be 1 ? (1 ? α)^1/4.     

Calcium complex of 2,5-dihydroxybenzoic acid (gentisic acid): synthesis,crystal structure,and spectroscopic properties

The synthesis, crystal structure, and spectral characteristics (IR, Raman, and ¹H and ¹³C NMR) of a monomeric hexa(aqua)calcium compound, viz. [Ca(C₇H₅O₄)₂(H₂O)₆]·H₂O (C₇H₅O₄ = 2,5-dihydroxybenzoate), are reported. The central Ca(II) located on a twofold axis is eight coordinate in an approximate square antiprismatic environment, bonded to two monodentate 2,5-dihydroxybenzoate ligands via the carboxylate oxygen, and six waters. The adjacent monomeric units are linked with the aid of several O–H?O hydrogen bonds.     

Aqueous Reactive Oxygen Species Induced by He + O<Subscript>2</Subscript> Plasmas: Chemistry Pathways and Dosage Control Approaches

Plasma–liquid interaction has already been a hotspot in the research field of plasma medicine. Aqueous reactive oxygen species (ROS) generated in this process are widely accepted playing a crucial role in plasma biomedical effects. In this paper, chemistry pathways among various aqueous ROS induced by He + O₂ plasmas are investigated by a numerical model. Simulation results show that these aqueous ROS can be classified into two groups according to their production ways: the group of species including O, ¹O₂ and e directly produced in plasma, and the other group of species including O₂ ^?, H₂O₂, O₃, etc. produced by liquid reactions. A key reaction chain of e → O₂ ^? → HO₂(→ HO₂ ^?) → H₂O₂ is found to be important in the plasma-induced liquid chemistry. Furthermore, impacts of changes in plasma and solution conditions on aqueous ROS concentrations are studied as well. It is found that changes in plasma conditions (O₂ ratio in the discharge gas/power density) can globally influence the concentrations of almost every aqueous ROS, while conditions changes of the treated liquid (pH/dissolved oxygen) only partially influence the concentrations of some specific species including O₂ ^?/HO₂, O₃ ^?/HO₃ and H₂O₂. The revelations of the liquid chemistry pathways and the dependence of ROS dosage on the treatment conditions offer a better understanding on the plasma–liquid interactions, as well as provide optimized dosage control approaches for biomedical applications.     

Production of Hydrogen-Rich Syngas from Biogas Reforming with Partial Oxidation Using a Multi-Stage AC Gliding Arc System

The aim of this research work was to evaluate the possibility of upgrading the simulated biogas (70?% CH₄ and 30?% CO₂) for hydrogen-rich syngas production using a multi-stage AC gliding arc system. The results showed that increasing stage number of plasma reactors, applied voltage and electrode gap distance enhanced both CH₄ and CO₂ conversions, in contrast with the increases in feed flow rate and input frequency. The gaseous products were mainly H₂ and CO, with small amounts of C₂H₂, C₂H₄ and C₂H₆. The optimum conditions for hydrogen-rich syngas production using the four-stage AC gliding arc system were a feed flow rate of 150?cm³/min, an input frequency of 300?Hz, an applied voltage of 17?kV and an electrode gap distance of 6?mm. At the minimum power consumption (3.3?×?10^?18?W?s/molecule of biogas converted and 2.8?×?10^?18?W?s/molecule of syngas produced), CH₄ and CO₂ conversions were 21.5 and 5.7?%, respectively, H₂ and CO selectivities were 57.1 and 14.9?%, respectively, and H₂/CO (hydrogen-rich syngas) was 6.9. The combination of the plasma reforming and partial oxidation provided remarkable improvements to the overall process performance, especially in terms of reducing both the power consumption and the carbon formation on the electrode surface but the produced syngas had a much lower H₂/CO ratio, depending on the oxygen/methane feed molar ratio. The best feed molar ratio of O₂-to-CH₄ ratio was found to be 0.3/1, providing the CH₄ conversion of 81.4?%, CO₂ conversion of 49.3?%, O₂ conversion of 92.4?%, H₂ selectivity of 49.5?%, CO selectivity of 49.96?%, and H₂/CO of 1.6.     

Synthesis and Solid-State Structure of Cyclobutyltellurium(IV)-Containing Dimeric Tungstoarsenates(III)

The cage-like cyclobutyltellurium(IV)-containing tungstoarsenate(III) dimers [(C₄H₈Te-OH)₂(C₄H₈Te)₆{As₂W₁₇O₆₁(H₂O)}₂]^14? (1) and [{(C₄H₈Te)₂W₂O₅(H₂O)₂As₂W₁₉O₆₇(H₂O)}₂]^16? (2) were synthesized in moderately acidic aqueous medium by reaction of C₄H₈TeI₂ with the lacunary tungstoarsenates(III) [B-α-AsW₉O₃₃]^9? and [As₂W₁₉O₆₇(H₂O)]^14?, respectively. Polyanion 1 was isolated as a mixed cesium-guanidinium salt Cs_8.5(C(NH₂)₃)_5.5[(C₄H₈TeOH)₂(C₄H₈Te)₆{As₂W₁₇O₆₁(H₂O)}₂]·60H₂O (1a), whereas 2 crystallized as a mixed cesium-potassium salt Cs₉K₇[{(C₄H₈Te)₂W₂O₅(H₂O)₂As₂W₁₉O₆₇(H₂O)}₂]·90H₂O (2a). Single crystal X-ray analysis demonstrated that 1a and 2a crystallized in the triclinic space group \( P \bar{1} \), with a = 12.7738(8) Å, b = 18.7490(14) Å, c = 21.9831(14) Å, α = 111.155(4)^o, β = 93.312(3)^o, γ = 99.530(4) and Z = 1 for 1a and a = 19.309(6) Å, b = 24.674(8) Å, c = 26.071(8) Å, α = 63.218(17)°, β = 89.26(16)^°, γ = 79.948(17)^° and Z = 2 for 2a. The polyanion salts 1a and 2a were characterized by solid state NMR (¹H, ¹³C, ¹²⁵Te), FT-IR, TGA-DSC, and elemental analysis.     

Synthese und Kristallstruktur von Blei(II)‐oxidhalogenid‐Alkoholaten mit unterschiedlichen Verknüpfungsvarianten von Pb4O4‐Heterokubaneinheiten

Synthesis and Crystal Structure Determination of Lead(II) Oxide Halide Alcoholates with Different Connectivity of Pb₄O₄ Heterocubane‐like Subunits The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl^? and Br^?) with diethylene glycole at a temperature of 180 °C leads to the isotypic compounds [Pb₆(C₄H₈O₃)O₂Cl₆] (1) and [Pb₆(C₄H₈O₃)O₂Br₆] (2) . In a similar synthesis with PbI₂ as educt at temperature of 160 °C the two modifications β‐[Pb₆(C₄H₈O₃)O₂I₆] (3) and α‐[Pb₆(C₄H₈O₃)O₂I₆] (4) were found, whereas at a reaction temperature of 180 °C [Pb₉(C₂H₄O₂)(C₄H₈O₃)O₃I₈] (5) was surprisingly obtained as product. The X‐ray diffraction data show that at a temperature of 180 °C a splitting of the ether took place. The cited compounds show cubane like subunits built by lead and oxygen atoms. These fragments are connected by alkoholate molecules. In 5 additionally an I₆ octahedra centered by lead is observed.     

Hydrothermal Synthesis,Crystal Structure,and Catalytic Performance of Four Organic–Inorganic Hybrids Based on Polyoxometalates and O/N-Containing Groups

Four new network organic–inorganic hybrid supramolecular compounds [PW₁₂O₄₀](C₂H₄N₃)₃·6H₂O (1), [PMo₁₂O₄₀](C₂H₄N₃)₃·6H₂O (2), [H₄SiW₁₂O₄₀]₈[C₆NO₂H₄]₄[C₆NO₂H₅]₁₆[C₅NH₆]₄·39H₂O (3) and [H₃VW₁₂O₄₀] (C₆H₆NO₂)₂(CHO₂)₂·4H₂O (4) composed by keggin type heteropolyanion and O/N-containing organic groups of 1H-1,2,4-Triazole or 2,3-Pyridinedicarboxylic acid have been successfully synthesized by hydrothermally method, and characterized by infrared spectrum (IR), thermogravimetric–differentialthermal analysis (TG–DTA), cyclic voltammetry (CV) and single crystal X-ray diffraction (XRD). Compounds 1–4 exhibit three dimensional supramolecular network via hydrogen bonds and/or π–π stacking interactions. These compounds exhibit good thermal stability and catalytic ability. They are active for catalytic oxidation of methanol in a continuous-flow fixed-bed micro-reactor, when the initial concentration of methanol is 2.5 g m^?3 in air and flow rate is 10 mL min^?1, the corresponding elimination rates of methanol are 65% (125 °C), 85% (125 °C), 94% (150 °C), and 80% (125 °C), respectively.     

Chemical Composition,Physical Properties and Populating Mechanism of Some O(I) States for a DC Discharge in Oxygen with Water Cathode

This paper reports the results of the experimental study of parameters for a DC oxygen discharge with water cathode in the pressure range of 0.1–1 bar and the discharge current of 40 mA. The radius of positive column, the cathode voltage drop, the cathode current density and the electric field strength were measured. Rotational temperatures of N₂ (C³Π_u, V = 0) and OH (A²Σ, V = 0) and absolute line intensities of atomic oxygen with wave length of 845 and 777 nm were determined as well. Plasma composition modeling was carried out by the combined solution of the Boltzmann equation for electrons, the equations of vibrational kinetics for ground states of N₂, O₂, H₂O molecules, and the equations of chemical kinetics, and the plasma conductivity equation. Calculations were carried out taking into consideration the discharge radial heterogeneity and using experimental values of E/N and gas temperatures. The main particles being formed in plasma were shown to be ^·OH, H₂O₂, O(³P), O₂(a¹Δ_g), O₂(b¹Σ _g ⁺ ), H(¹S). On the basis of this calculation and experimental values of line intensities, the populating mechanism of (3p ³P) level of atomic oxygen was discussed. The comparison of some properties of discharges in O₂, N₂ and air was done.     

Einfach und doppelt deprotonierte Maleinsäure in Praseodym‐hydrogenmaleat‐octahydrat,Pr(C4O4H3)3 · 8 H2O,und Praseodym‐maleatchlorid‐tetrahydrat,Pr(C4O4H2)Cl · 4 H2O

Single and Double Deprotonated Maleic Acid in Praseodymium Hydrogenmaleate Octahydrate, Pr(C₄O₄H₃)₃ · 8 H₂O, and Praseodymiummaleatechloride Tetrahydrate, Pr(C₄O₄H₂)Cl · 4 H₂O Single crystals of Pr(C₄O₄H₃)₃ · 8 H₂O grew by slow evaporation of a solution which had been obtained by dissolving Pr(OH)₃ in aqueous maleic acid. The triclinic compound (P1, Z = 2, a = 728.63(3), b = 1040.23(3), c = 1676.05(8) pm, α = 72.108(2)°, β = 87.774(2)°, γ = 70.851(2)°, R_all = 0.0261) contains Pr³⁺ ions in ninefold coordination of oxygen atoms which belong to two monodentate maleate ions and seven H₂O molecules. There is one further non‐coordinating maleate ion and one crystal water molecule in the unit cell. Thermal treatment of Pr(C₄O₄H₃)₃ · 8 H₂O leads first to the anhydrous compound which then decomposes to the respective oxide in two steps upon further heating. Evaporation of a solution of Pr(C₄O₄H₃)₃ · 8 H₂O which contained additional Cl^– ions yielded single crystals of Pr(C₄O₄H₂)Cl · 4 H₂O. In the crystal structure (monoclinic, P2₁/c, Z = 4, a = 866.0(1), b = 1344.3(1), c = 896.9(1) pm, β = 94.48(2)°, R_all = 0.0227), the Pr³⁺ ions are surrounded by nine oxygen atoms. The latter belong to four H₂O molecules and three maleate ions. Two of the latter act as bidentate ligands.     

A sandwich-type POM containing mixed cations: synthesis,thermal performance and proton-conducting properties

A new sandwich-type polyoxometalate, Na₅H[N(CH₃)₄]₂[Co(C₃N₂H₄)₂(H₂O)₄][Co₄(H₂O)₂(PW₉O₃₄)₂]·21H₂O (1), has been synthesized. 1 is composed of a Weakley-type polyanion, [Co₄₍H₂O)₂(PW₉O₃₄)₂]^10?, four kinds of cations (five Na⁺, two [N(CH₃)₄]⁺, one [Co(C₃N₂H₄)₂(H₂O)₄]²⁺, and one H⁺), and 21 crystalline H₂O molecules. The surface oxygen of the polyanion in 1, the crystalline water, and coordinated water molecules make an extended 3-D hydrogen-bonding network. Alternating current (AC) impedance experiments of 1 reveal good proton conductivity for 1 of 5.03 × 10^??4 S cm^?1 at 25 °C under 98% relative humidity (RH). Activation energy of 1 calculated from Arrhenius plots is 0.358 eV, indicating Grotthuss mechanism is dominant in the proton transfer. Thermal decomposition behavior of 1 was examined by thermogravimetry/mass spectrometry (TG/MS) measurements.