Search

The investigation of the coordination chemistry of heterometallic transition-metal complexes of palladium (Pd) and rhenium (Re) led to the isolation and crystallographic characterization of tetra­kis­(1,3-di­methyl­imidazolium-2-yl­idene)palladium(II) hexa­deca­carbonyl­tetra­rhenium diethyl ether disolvate, [Pd(C5H8N2)4][Re4(CO)16]·2C4H10O or [Pd(IMe)4][Re4(CO)16]·2C4H10O, (1), and di­carbonyl­octa-μ-carbonyl-tetra­kis­(tri­phenyl­phosphane)palladiumdirhenium, [Pd4Re2(C18H15P)4(CO)10] or Pd4Re2(PPh3)4(μ-CO)8(CO)2, (2), from the reaction of Pd(PPh3)4 with 1,3-di­methyl­imidazolium-2-carboxyl­ate and Re2(CO)10 in a toluene–aceto­nitrile mixture., The investigation of the coordination chemistry of heterometallic transition-metal complexes of palladium (Pd) and rhenium (Re) led to the isolation and crystallographic characterization of tetra­kis­(1,3-di­methyl­imidazolium-2-yl­idene)palladium(II) hexa­deca­carbonyl­tetra­rhenium diethyl ether disolvate, [Pd(C5H8N2)4][Re4(CO)16]·2C4H10O or [Pd(IMe)4][Re4(CO)16]·2C4H10O, (1), and octa-μ-carbonyl-di­carbonyl­tetra­kis­(tri­phenyl­phosphane)palladium­dirhenium, [Pd4Re2(C18H15P)4(CO)10] or Pd4Re2(PPh3)4(μ-CO)8(CO)2, (2), from the reaction of Pd(PPh3)4 with 1,3-di­methyl­imidazolium-2-carboxyl­ate and Re2(CO)10 in a toluene–aceto­nitrile mixture. In complex 1 the Re—Re bond lengths [2.9767 (3)–3.0133 (2) Å] are close to double the covalent Re radii (1.51 Å). The palladium–rhenium carbonyl cluster 2 has not been structurally characterized previously; the Pd—Re bond lengths [2.7582 (2)–2.7796 (2) Å] are about 0.1 Å shorter than the sum of the covalent Pd and Re radii (1.39 + 1.51 = 2.90 Å). One carbene ligand and a diethyl ether mol­ecule are disordered over two positions with occupancy ratios of 0.5:0.5 and 0.625 (15):0.375 (15) in 1. An unidentified solvent is present in compound 2. The given chemical formula and other crystal data do not take into account the unknown solvent mol­ecule(s). The SQUEEZE routine [Spek (2015 ▸). Acta Cryst. C71, 9–18] in PLATON was used to remove the contribution of the electron density in the solvent region from the intensity data and the solvent-free model was employed for the final refinement. The cavity with a volume of ca 311 Å3 contains approximately 98 electrons.

The reaction of tris(2-methoxy-5-chlorophenyl)antimony with pentafluoropropionic, heptafluorobutanoic, pentafluorobenzoic, or 2-methoxybenzoic acids in the presence of hydrogen peroxide (1 : 2 : 1 molar ratio) in diethyl ether has afforded tris(2-methoxy-5-chlorophenyl)antimony dicarboxylates (2-MeO-5-ClC6H3)3Sb[OC(O)R]2, R = C2F5, C3F7, C6F5, or C6H4ОMe-2. Structures of the synthesized compounds have been investigated.

This study aims to convert ethanol to higher value-added products, particularly diethyl ether and ethylene using the catalytic dehydration of ethanol. Hence, the gas-phase dehydration of ethanol over Al2O3-HAP catalysts as such and modified by addition of palladium (Pd) in a microreactor was evaluated. The commercial Al2O3–HAP catalyst was first prepared by the physical mixing method, and then, the optimal ratio of the Al2O3–HAP catalyst (2:8 by wt %) was impregnated with Pd to develop a new functional catalyst to alter surface acidity. Based on the results, the combination of Al2O3 and HAP catalysts generated significant quantities of weak acid sites which demonstrates an enhancement in catalytic activity. In addition, Pd modification in the optimal composition ratio of the Al2O3–HAP catalyst extremely increased the amount of weak acid sites as well as weak acid density due to the synergistic effect between the Pd and Al2O3–HAP catalyst that are supposed to suggest the active sites in the reaction. Among all catalysts, the Al20-HAP80-Pd catalyst displayed brilliant catalytic performance in the course of diethyl ether yield (ca. 51.0%) at a reaction temperature of 350 °C and ethylene yield (ca. 75.0%) at a reaction temperature of 400 °C having an outstanding stability under time-on-stream for 10 h. This is recognized to the combination of the effects of weak acid sites (Lewis acidity), small amount of strong acid sites, and structural characteristics of the catalytic materials used.

The reaction of the vanadium(III) tris(silylamide) V{N(SiMe3)2}3 with LiAlH4 in diethyl ether gives the highly unstable mixed-metal polyhydride [V(μ2-H)6[Al{N(SiMe3)2}2]3][Li(OEt2)3] (1), which was structurally characterized. Alternatively, performing the same reaction in the presence of 12-crown-4 affords a rare example of a structurally verified vanadium terminal hydride complex, [VH{N(SiMe3)2}3][Li(12-crown-4)2] (2). The corresponding deuteride 2D was also prepared using LiAlD4. In contrast, no hydride complexes were isolated by reaction of M{N(SiMe3)2}3 (M = Cr, Fe) with LiAlH4 and 12-crown-4. Instead, these reactions afforded the anionic metal(II) complexes [M{N(SiMe3)2}3][Li(12-crown-4)2] (3, M = Cr; 4, M = Fe). The reaction of the iron(III) tris(silylamide) Fe{N(SiMe3)2}3 with lithium aluminum hydride without a crown ether gives the "hydrido inverse crown" complex [Fe(μ2-H){N(SiMe3)2}2(μ2-Li)]2 (5), while treatment of the same trisamide with alane trimethylamine complex gives the iron(II) polyhydride complex Fe(μ2-H)6[Al{N(SiMe3)2}2]2[Al{N(SiMe3)2}(NMe3)] (6). Complexes 2-6 were characterized by X-ray crystallography, as well as by infrared, electronic, and 1H and 13C (complex 6) NMR spectroscopies. Complexes 1 and 6 are apparently formed by an unusual "metallo-transamination" process.

We describe the preparation of the cis-bis(η1,η2-2,2-dimethylpent-4-en-1-yl)rhodate(I) anion, cis-[Rh(CH2CMe2CH2CH═CH2)2]-, and the interaction of this species with Li+ both in solution and in the solid state. For the lithium(diethyl ether) salt [Li(Et2O)][Rh(CH2CMe2CH2CH═CH2)2], VT-NMR and 1H{7Li} NOE NMR studies in toluene-d8 show that the Li+ cation is in close proximity to the dz2 orbital of rhodium. In the solid-state structure of the lithium(12-crown-4) salt [Li(12-crown-4)2][Li{Rh(CH2CMe2CH2CH═CH2)2}2], one lithium atom is surrounded by two [Rh(CH2CMe2CH2CH═CH2)2]- anions, and in this assembly there are two unusually short Rh-Li distances of 2.48 A. DFT calculations, natural energy decomposition, and ETS-NOCV analysis suggest that there is a weak dative interaction between the 4dz2 orbitals on the Rh centers and the 2pz orbital of the Li+ cation. The charge-transfer term between Rh and Li+ contributes only about the 1/5 of the total interaction energy, however, and the principal driving force for the proximity of Rh and Li in compounds 1 and 2 is that Li+ is electrostatically attracted to negative charges on the dialkylrhodiate anions.

Low-valent uranium coordination chemistry continues to rely heavily on access to trivalent starting materials, but these reagents are typically prepared from uranium turnings, which are becoming increasingly difficult to acquire. Here we report convenient syntheses of UI3(THF)4 (THF = tetrahydrofuran) and UBr3(THF)4 from UCl4, a more accessible uranium starting material that can be prepared from commercially available uranium oxides. UCl3(THF)2 (1), UBr3(THF)4 (2), and UI3(THF)4 (3) were prepared by single-pot reductions from UCl4 using KH and KC8 and converted to 2 or 3 by halide exchange with the corresponding Me3SiX (where X = Br or I). Reduction of UI4(Et2O)2 (4; Et2O = diethyl ether) and UI4(1,4-dioxane)2 (5) was also shown to cleanly yield 3. Complex 1 was also synthesized separately by the addition of anhydrous HCl to U(BH4)3(THF)2, which was prepared by thermal reduction of U(BH4)4. All three trivalent uranium halide complexes were isolated in high crystalline yields (typically 85-99%) and their formulations were confirmed by single-crystal X-ray diffraction, elemental analysis, and 1H NMR and IR spectroscopy. Elemental analysis conducted on triplicate samples of 1-3 exposed to vacuum for different time intervals revealed significant THF loss for all three complexes in as little as 15 min. Overall, these results offer expedient entry into low-valent uranium chemistry for researchers lacking access to uranium turnings.

Bismuth compounds Ph3Bi[OC(O)R]2 (R = CH2C6H4F-3, C6H3F2-2,3, C6HF4-2,3,4,5) were synthesized by the reaction of triphenylbismuth with a carboxylic acid and tert-butyl hydroperoxide (1 : 2 : 1 mol.) in diethyl ether. Structural features of these compounds were determined by the single crystal X-ray analysis method. Bismuth atoms in triphenylbismuth dicarboxylates have distorted trigonal-bipyramidal coordination with oxygen atoms in axial positions. The presence of intramolecular contacts Bi···O(=C) [2.833(8)–3.136(9) A] causes an increase in one of CBiC bond angles to 151.07(15)°, 142.0(3)°, 138.53(14)°, respectively, due to a decrease in the other two angles.

The hydrolysis of the tetrasodium salt of dpp-bian (dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) affords the organic compound 1,6,7,8-H4-dpp-bian (1). This reaction is accompanied by the protonation of the nitrogen atom of the diimine moiety and one ring of the naphthalene system of the molecule. The reduction of 1 with one equivalent or an excess of sodium metal in 1,2-dimethoxyethane gives the salts [(6,7,8-H3-dpp-bian)Na(dme)2] (2a) and [(5,6,7,8-H4-dpp-bian)Na2(dme)2] (3), respectively. The exchange reaction of compound 1 with one equivalent of sodium amide in diethyl ether affords the monosodium salt [(6,7,8-H3-dpp-bian)Na(Et2O)2] (2b). Compounds 1–3 were characterized by NMR and IR spectroscopy and elemental analysis. The molecular structures of 1–3 were determined by X-ray diffraction.

Tris(m-tolyl)antimony dicarboxylates (3-MeC6H4)3Sb[OC(O)CH2Cl]2 and (3-MeC6H4)3Sb[OC(O)C6H3F2-2,3]2 were synthesized by the reaction of tris(m-tolyl)antimony with chloroacetic and 2,3-difluorobenzoic acids in the presence of tert-butyl hydroperoxide (molar ratio 1 : 2 : 1, respectively) in diethyl ether. Under similar conditions, the reaction of tris(m-tolyl)antimony with 2,4-dinitrobenzenesulfonic acid leads to the formation of µ-oxobis-[tris(m-tolyl)(2,4-dinitrobenzenesulfonato)antimony]. The Sb atoms in the resulting compounds have distorted trigonal-bipyramidal coordination with electronegative ligands in axial positions.

Addition of 2-adamantylMgBr in diethyl ether to Mo(NArF)2(Cl)2(DME) (ArF = C6F5) gave Mo(NArF)2(Ad)2 (2, Ad = 2-adamantyl, DME = 1,2-dimethoxyethane). Addition of HCl and 2,2′-bipyridyl (bipy) to 2...

The reaction of Cr(NO3)3·9H2O with potassium cyclobutane-1,1-dicarboxylate (K2(Cbdc)) in 1 : 3 ratio was studied. It was shown that, depending on the reaction conditions and the solvents used for synthesis and crystallization, compounds of various compositions and structures can be isolated from the reaction system. Conducting the reaction in water followed by recrystallization from ethanol and methanol results in isolation of 2D polymeric complexes [KCr(Cbdc)2(H2O)2]n (I) and {[K4Cr2(OMe)2(Cbdc)4(MeOH)6]· MeOH}n (II), respectively. The addition of excess KOH to the same reaction mixture and recrystallization from alcohols gives rise to the crystals of 3D polymeric compound [K3Cr(Cbdc)3(H2O)2]n (III). Conducting the reaction in methanol followed by slow diffusion of diethyl ether affords complex [K3Cr(Cbdc)3(MeOH)2(H2O)2]n (IV) with a 2D polymeric structure. The crystal structures of compounds I–IV were determined by X-ray diffraction (CIF files CCDC nos. 2006090 (I), 2006109 (II), 2006116 (III), and 2 006 117 (IV)).

The present work aims to investigate the effect adding Ag, Co, Ni, Cd and Pt to copper on ethanol dehydrogenation. The catalysts synthesized by deposition–precipitation method were characterized using various physicochemical methods such as N2 adsorption–desorption, TPR, SEM–EDX, XRD, XPS and TGA–DSC-MS. Catalytic evaluation results revealed that the predominant product of the reaction was acetaldehyde. Monometallic copper or mixed with Cd, Ag or Co show good catalytic performances. Adding nickel to copper improves the process conversion but reduces acetaldehyde selectivity, giving rise to methane in produced hydrogen. Pt-Cu/SiO2 catalyst guides the reaction towards diethyl ether. Time on stream tests performed during 12 h at 260 °C, showed that adding Cd to Cu enhances its stability by over 30% of conversion, this is explained by the reduction of copper crystallites sintering, which makes Cd-Cu/SiO2 a promising catalyst for the production of acetaldehyde by ethanol dehydrogenation.

Raising the coulombic efficiency of lithium metal anode cycling is the deciding step in realizing long-life rechargeable lithium batteries. Here, we designed a highly concentrated salt/ether electrolyte diluted in a fluorinated ether: 1.8 M LiFSI in DEE/BTFE (diethyl ether/bis(2,2,2-trifluoroethyl)ether), which realized an average coulombic efficiency of 99.37% at 0.5 mA cm−2 and 1 mAh cm−2 for more than 900 cycles. This electrolyte also maintained a record coulombic efficiency of 98.7% at 10 mA cm−2, indicative of its ability to provide fast-charging with high cathode loadings. Morphological studies reveal dense, dendrite free Li depositions after prolonged cycling, while surface analyses confirmed the formation of a robust LiF-rich SEI layer on the cycled Li surface. Moreover, we discovered that this ether-based electrolyte is highly compatible with the low-cost, high-capacity SPAN (Sulfurized polyacrylonitrile) cathode, where the constructed Li||SPAN cell exhibited reversible cathode capacity of 579 mAh g−1 and no capacity decay after 1200 cycles. A cell where a high areal loading SPAN electrode (>3.5 mAh cm−2) is paired with only onefold excess Li was constructed and cycled at 1.75 mA cm−2, maintaining a coulombic efficiency of 99.30% for the lithium metal. Computational simulations revealed that at saturation, the Li-FSI complex forms contact ion pairs, with a first solvation shell comprising DEE molecules, and a second solvation shell with a mix of DEE/BTFE. This study provides a path to enable high energy density Li||SPAN batteries with stable cycling.

Ammonia (NH3) is recognized as a carbon-free hydrogen-carrier fuel with a high content of hydrogen atoms per unit volume. Recently, ammonia has received increasing attention as a promising alternative fuel for internal combustion engine and gas turbine applications. However, the viability of ammonia fueling future combustion devices has several barriers to overcome. To overcome the challenge of its low reactivity, it is proposed to blend it with a high-reactivity fuel. In this work, we have investigated the combustion characteristics of ammonia/diethyl ether (NH3/DEE) blends using a rapid compression machine (RCM) and a constant volume spherical reactor (CVSR). Ignition delay times (IDTs) of NH3/DEE blends were measured using the RCM over a temperature range of 620 to 942 K, pressures near 20 and 40 bar, equivalence ratios (Φ) of 1 and 0.5, and a range of mole fractions of DEE, χDEE, from 0.05 to 0.2 (DEE/NH3 = 5 – 20%). Laminar burning velocities of NH3/DEE premixed flames were measured using the CVSR at 298 K, 1 bar, Φ of 0.9 to 1.3, and χDEE from 0.1 to 0.4. Our results indicate that DEE promotes the reactivity of fuel blends resulting in significant shortening of the ignition delay times of ammonia under RCM conditions. IDTs expectedly exhibited strong dependence on pressure and equivalence ratio for a given blend. Laminar burning velocity was found to increase with increasing fraction of DEE. The burnt gas Markstein length increased with equivalence ratio for χDEE = 0.1 as seen in NH3-air flames, while the opposite evolution of Markstein length was observed with Φ for 0.1

The prospects of using cerium as a modifying additive of Mg–Al hydrotalcite-derived oxide system have been estimated by low-temperature nitrogen ad(de)sorption, X-ray diffraction, scanning electron microscopy, 1H and 27Al solid-state nuclear magnetic resonance (NMR), X-ray photoelectron and UV–Vis diffuse reflectance spectroscopy techniques. The effect of such tuning of structural-textural characteristics and acid–base properties of the surface on its catalytic performance in ethanol conversion has been studied. Solid-state NMR spectroscopic study of the probe molecule adsorption and temperature-programmed desorption of NH3 and CO2 with mass-spectrometry control are used to determine the nature and strength distribution of acidic and basic sites of Mg–Al(–Ce) oxide systems. It has been found that the selectivity towards 1-butanol up to 68.1% (548 K) is achieved in ethanol conversion over Mg–Al–Ce sample at time-on-stream ≤ 2 h. At higher time-on-stream, the specific rates of the target product (1-butanol) formation are comparable for both modified and un-modified catalysts, but the products distribution differs. Cerium modification of Mg–Al oxide catalyst leads to increase in specific rate of acetaldehyde formation due to increase in the number of basic sites and their surface density. Wherein, the rate of ethanol dehydration products (ethylene and diethyl ether) is reduced, apparently, due to decrease in a number of Lewis acidic sites formed by Al3+ cations octahedrally coordinated to oxygen.

In this article, we investigated the I2-promoted cyclic dialkyl ether formation from 6-membered oxanickelacycles originally reported by Hillhouse. A detailed mechanistic investigation based on spectroscopic and crystallographic analysis revealed that a putative reductive elimination to forge C(sp3)–OC(sp3) using I2 might not be operative. We isolated a paramagnetic bimetallic NiIII intermediate featuring a unique Ni2(OR)2 (OR = alkoxide) diamond-like core complemented by a μ-iodo bridge between the two Ni centers, which remains stable at low temperatures, thus permitting its characterization by NMR, EPR, X-ray, and HRMS. At higher temperatures (>−10 °C), such bimetallic intermediate thermally decomposes to afford large amounts of elimination products together with iodoalkanols. Observation of the latter suggests that a C(sp3)–I bond reductive elimination occurs preferentially to any other challenging C–O bond reductive elimination. Formation of cyclized THF rings is then believed to occur through cyclization of an alcohol/alkoxide to the recently forged C(sp3)–I bond. The results of this article indicate that the use of F+ oxidants permits the challenging C(sp3)–OC(sp3) bond formation at a high-valent nickel center to proceed in good yields while minimizing deleterious elimination reactions. Preliminary investigations suggest the involvement of a high-valent bimetallic NiIII intermediate which rapidly extrudes the C–O bond product at remarkably low temperatures. The new set of conditions permitted the elusive synthesis of diethyl ether through reductive elimination, a remarkable feature currently beyond the scope of Ni.

Hydrothermal treatment for dairy manure into value-added hydrochar and bio-oil is a potential technology for its resource utilization. During the process of treatment, extractant is applied to the separation of hydrochar and bio-oil. In this study, three polar extractants (ethyl acetate, dichloromethane, diethyl ether) and two nonpolar extractants (n-hexane and petroleum ether) were used, and the physico-chemical properties of hydrochar and the composition of bio-oil were investigated. Compared with nonpolar extractants, polar extractants could extract the bio-oil absorbed on the hydrochar exterior and interior surface, resulting in more mass loss of hydrochar and better extraction performance on the production of bio-oil. The decrease of H/C atomic ratio and the increase of O/C atomic ratio indicated the demethanation tendency to occur during the extraction process, and enhanced the hydrochar stability. The scanning electron microscope and specific surface area analysis revealed that polar extractant had a more positive effect than nonpolar extractant on the occurrence of disperse spherical microparticles and the augment of hydrochar specific surface area. The bio-oil from polar extractant mainly consisted of N-containing compounds, ketones, phenols and acids, while the bio-oil from nonpolar extractant mainly consisted of esters, alkanes and aromatics. These results reveal that the hydrochar extracted by polar solvent exerts a greater potential for the production of carbon-based material.

The reaction of 2-methoxy-5-chlorophenyllithium with SbCl3 (3 : 1) in diethyl ether has afforded tris(2-methoxy-5-chlorophenyl)antimony, which has been crystallized from benzene as solvate. Treatment of the solvate with bromine in chloroform has led to the formation of tris(2-methoxy-5-chlorophenyl)antimony dibromide, which has been isolated from benzene as solvate as well. The product of a similar reaction with chlorine, tris(2-methoxy-5-chlorophenyl)antimony dichloride, has been also obtained via oxidation of tris(2-methoxy-5-chlorophenyl)antimony with copper dichloride in acetone. The structural features of the obtained compounds have been established by means of single-crystal X-ray diffraction analysis.

Mid-infrared spectra for C-D···O hydrogen (H)-bonded binary complexes of CDCl3 with acetone (AC), cyclohexanone (CHN), diethyl ether (DEE), and tetrahydrofuran (THF) have been measured in the vapor phase at room temperature and in an argon matrix at 8 K. Remarkable matrix effect has been observed in each case with respect to the spectral shift of the donor group's stretching fundamental (ΔνC-D). In the case of complexes with AC and CHN, the sign of ΔνC-D changes from a few wavenumbers positive (blue shift) in the vapor phase to a few tens of wavenumbers negative (red shift) in the argon matrix. For the two ether complexes, although no apparent reversal in the sign of ΔνC-D occurs, but the magnitudes of the red shifts in the matrix are manifold larger, and the bands appear with large enhancement in transition intensity. The medium effect has been explained consistently in terms of the local hyperconjugative charge transfer interaction at the H-bonding sites of the complexes and its interplay with the H-bond distance that varies with the physical conditions of the medium. Under the matrix isolation condition, νC-D bands of CHN and THF complexes depict a large number of substructures, which has been interpreted in terms of matrix site effect as well as Fermi resonance enhancement of the fingerprint combination tones and trapping of more than one isomer of the complexes in the matrix sites.

The catalytic conversion of ethanol to butanol and butadiene at 633 K and atmospheric pressure (7 vol% ethanol) was studied over calcium phosphate materials pretreated over a wide temperature range. For calcium phosphate pretreated at or below 923 K, the resulting solid had an apatite structure identified by X-ray diffraction and strong acid sites probed by triethylamine (TEA) adsorption microcalorimetry. The low temperature pretreated materials were not effective at ethanol coupling reactions but instead were highly selective to acid-catalyzed products ethene and diethyl ether. Pretreatment of calcium phosphate at 973 K transformed the apatite structure to β-tricalcium phosphate, which exposed both acid and base sites evaluated by TEA and CO2 adsorption microcalorimetry. High temperature pretreated calcium phosphate catalysts formed the coupling products butanol and butadiene during ethanol reaction. The butadiene selectivity was improved by supporting calcium phosphate on zirconia. The influence of catalyst structure on the activity and selectivity of calcium phosphates was elucidated for the conversion of ethanol.

Addition of 2-adamantylMgBr in diethyl ether to Mo(NAr)2(Cl)2(DME) (Ar = 2,6-i-Pr2C6H3) gave Mo(NAr)2(2-Ad)2 (2-Ad = 2-adamantyl, DME = 1,2-dimethoxyethane), from which Mo(NAr)(Adene)(OTf)2(DME) (1...

The application of hydrogen energy urgently requires a high-capacity hydrogen storage technology that can release hydrogen at low temperature. The composite of LiAlH4 and NH4F has a hydrogen storage capacity of up to 8.06 wt%, but the release of hydrogen requires a reaction temperature of about 170 °C, and the reaction is difficult to control. In this work, the reaction between LiAlH4 and NH4F is proposed to be carried out in diethyl ether to improve its hydrogen release performance. It exhibits good hydrogen release performance over a wide temperature range of −40–25 °C, and the hydrogen release capacity at −40 °C, −20 °C, 0 °C and 25 °C can reach 4.41 wt%, 6.79 wt%, 6.85 wt% and 7.78 wt%, respectively. The activation energy of the reaction is 38.41 kJ mol−1, which is much lower than many previously reported catalytic hydrolysis systems that can release hydrogen at room temperature. Our study demonstrates a high-performance hydrogen storage system with very low operating temperature, which may lay the foundation for the development of practical mobile/portable hydrogen source in the north and the Arctic.

This study aims to demonstrate the importance of using the 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM] [BF4] ionic liquid (IL) as a green solvent in the extractive desulfurization of commercial gasoline, as a complementary technology to conventional hydrodesulfurization (HDS), which has limitations in the removal of sulfur aromatic compounds. The extractive desulfurization of gasoline was evaluated by means of a factorial design to determine the best extraction conditions, considering temperature (25 and 35 °C), feed/solvent mass ratio (3/1 and 1/1) and number of extraction stages (1 and 3 stages). The results show a maximum sulfur removal efficiency of 40%. In addition, the selectivity of [BMIM] [BF4] in the removal of aromatic sulfur compounds from gasoline, its extraction mechanism and the effects of desulfurization using IL regenerated by means of washing cycles with water and/or diethyl ether was investigated.

Organophosphate compounds are widely used in industrial hydrometallurgical processes asextractants and complexones of non-ferrous, noble, rare-earth metals and transuranic elements. Among thesecompounds, organic phosphates occupy a special place, as they allow for the extraction processes with goodselectivity and efficiency. However, a significant drawback of known organic phosphates is their low extractioncapacity, as well as rather good solubility in water and their hydrolysability in aqueous acidic solutions, whichleads to both loss of the extractant and contamination of the extracted metal with organophosphorus compounds.Therefore, the search and development of new uranium effective extractants is an important task for thedevelopment of modern hydrometallurgical processes.This report describes the successful use of availablebis(2,2,2-trifluoroethyl)(2-cyanoethyl)phosphate, which is easily obtained from bis(2,2,2-trifluoroethyl)chlorophosphate and 3-hydroxypropanonitrile in the pyridine/diethyl ether system as an extractant of uraniumfrom uranium-containing acid solutions. For this functional phosphate containing a cyano group, one shouldexpect a synergistic effect of the extraction properties of the phosphates themselves, as well as of the knownextractants - contribute to an increase in its incombustibility.The purpose of this research is to develop the optimalconditions for the scaled synthesis of bis(2,2,2-trifluoroethyl)(2-cyanoethyl)phosphate, to accumulate its enlargedbatch and to study the extraction properties in the production process of uranium extraction from uranium-containingsulfate and nitric acid solutions.The research results showed that bis(2,2,2-trifluoroethyl)(2-cyanoethyl) phosphate,easily obtained from the available bis(2,2,2-trifluoroethyl) chlorophosphate and 3-hydroxypropanonitrile in thepyridine/diethyl ether system, exhibits pronounced extraction properties with respect to uranium. Thus, the use ofthis extractant in the production of the extraction of uranium from uranium-containing nitric acid or sulfuric acidsolutions was 20.7% and 18.7%; the content of uranium in the extractant was 63.9 g/dm3and 49. 7 g/dm3,respectively.Positive results were also obtained when studying the synergistic properties of the new extractant andthe traditional - bis(2-ethylhexyl) phosphate. Using a mixture of these extractants (their weight ratio was 1:1.2)allows you to extract 57% of uranium from the uranium sulphate solution. This is 9% more than in a similar processusing only bis(2-ethylhexyl) phosphate as an extractant. The use of bis(2,2,2-trifluoroethyl)(2-cyanoethyl) phosphateas a new extractant makes it possible to extract up to 20.7% of uranium from technological nitrate or sulphate ofuranium-containing solutions. With the combined use of bis(2,2,2-trifluoroethyl)(2-cyanoethyl) phosphate and theknown extractant bis(2-ethylhexyl) phosphate in this process, a synergistic effect is observed, which increases theefficiency of uranium extraction and improves the technological indicators of extraction.The extractantbis(2,2,2-trifluoroethyl)(2-cyanoethyl) phosphate works more efficiently in nitric acid solutions than in sulphate

Antisolvent-assisted crystallization is adopted widely in the preparation of double-cation [e.g., cesium/formamidinium (Cs/FA), formamidinium/methylammonium (FA/MA)] and triple-cation (e.g., Cs/FA/MA) FA-based perovskite solar cells (PSCs) to enhance their power conversion efficiencies (PCEs) and device stability. Although many antisolvents have been applied to treat various perovskites with different compositions, their crystallization mechanisms have remained unclear. In this study, we investigated the effects of a series of green antisolvents—namely, the ethers diethyl ether, anisole, diisopropyl ether (DIE), and dibutyl ether—on the crystallization of perovskites. We found that the formation of an intermediate phase was heavily determined by the antisolvent's polarity. Indeed, through judicious control of the antisolvent's polarity, it was possible to form a pure intermediate phase, without a PbI2 or perovskite phase. Upon thermal annealing, the crystallization of perovskites was improved. Understanding the mechanism of formation of the intermediate phase led us to identify DIE as a green antisolvent with universal perovskite compatibility, achieving champion PCEs of 20.05%, 20.15%, and 21.26% for Cs/FA, FA/MA, and Cs/FA/MA, respectively. The PCE of large-area (1 cm2) PSCs reached 18.51%. Furthermore, the repeatability of these champion PCEs was greatly improved. This work contributes to the understanding of antisolvent's polarity as an important factor affecting the formation of a pure intermediate phase of FA-based perovskites, which also offers a greener approach for the production of PSCs.

In the present work, the palladium (Pd) modification and supporting effect of W/TiO2 catalysts on catalytic ethanol dehydration to ethylene and diethyl ether were investigated. The Pd modification with different sequence of Pd and W impregnation on the catalysts was prepared by the incipient wetness impregnation technique. The catalyst characterization and activity testing revealed that the different sequence during impregnation influenced the physicochemical properties and ethanol conversion of catalyst. The differences in structure and surface properties were investigated by XRD, BET, SEM, EDX, XPS and NH3-TPD. Upon the reaction temperature between 200 to 400°C, it was found that the conversion increased with increasing of temperature for all catalysts. The Pd incorporated into catalysts enhanced the ethanol conversion depending on the sequence of impregnation. At low temperature (ca. 200 to 300°C), diethyl ether is a major product and the Pd modification over W/TiO2 catalyst resulted in increased diethyl ether yield. This is because an increase of ethanol conversion was obtained with Pd modification, while diethyl ether selectivity did not change. This can be attributed to the higher amount of weak acids sites present after Pd modification into catalyst. Among all catalysts, the PdW/TiO2 catalyst (coimpregnation) achieved the highest diethyl ether yield of 41.4% at 300℃. At high temperature (ca. 350 to 400°C), ethylene is the major product. The W/Pd/TiO2 catalyst (with sequential impregnation of Pd on TiO2 followed by W) exhibited the highest ethylene yield of 68.1% at 400°C. It can be concluded that the modification of Pd onto W/TiO2 upon different sequence of Pd and W impregnation can improve the diethyl ether and ethylene yield in catalytic ethanol dehydration.

The cation [Se(CH2C(O)CH3)3]+ represents the first example for a cationic selenium compound with three ketone functional groups located in the β-position with respect to the selenium atom. The cation possesses almost trigonal–pyramidal C 3 symmetry and forms hydrogen bonds to the ammonio group of the anion, The reaction of [Se8][B12F11NH3]2 with acetone and subsequent crystallization from acetone/diethyl ether yielded the selenium cation [Se(CH2C(O)CH3)3]+ as a by-product, which is stabilized by the weakly coordinating undeca­fluorinated anion [B12F11NH3]−. While attempting to crystallize pure [Se8][B12F11NH3]2, the structure of the isolated product, namely, tris­(2-oxoprop­yl)selenium 1-ammonio­undeca­fluoro­dodeca­borate, was surprising. The cation [Se(CH2C(O)CH3)3]+ represents the first example for a cationic selenium compound with three ketone functional groups located in the β-position with respect to the selenium atom. The cation possesses almost trigonal–pyramidal C 3 symmetry and forms hydrogen bonds to the ammonio group of the anion.

General volatile anaesthetics (GVA) inhibit electrical signal propagation in animal neurons. Although plants do not have neurons, they generate and propagate electrical signals systemically from a local damaged leaf to neighbouring leaves. This systemic electrical signal propagation is mediated by ligand-gated glutamate receptor-like (GLR) channels. Here, we investigated the effect of GVA diethyl ether on the systemic electrical and further downstream responses in Arabidopsis thaliana. We monitored electrical signals, cytoplasmic Ca2+ level ([Ca2+]cyt), ultra-weak photon emission, amino acid contents, phytohormone response as well as gene expression in response to heat wounding during diethyl ether anaesthesia. We found complete suppression of electrical and [Ca2+]cyt signal propagation from damaged leaf to neighbouring systemic leaves upon diethyl ether treatment. Concomitantly, jasmonates (JAs) did not accumulate and expression of JA-responsive genes (AOS, OPR3, JAZ10) was not detected in systemic leaves. However local damaged leaves still showed increased [Ca2+]cyt and accumulated high level of JAs and JA-inducible transcripts. An exogenously added GLR ligand, L-glutamate, was not able to trigger Ca2+ wave in etherized plants indicating that GLRs are targeted by diethyl ether, but not specifically. The fact that GVA inhibit electrical signal propagation not only in animals but also in plants is intriguing. However, the cellular response is completely blocked only in systemic leaves; the local damaged leaf still senses damaging stimuli.

A new type of dititanium dinitrogen complex supported by a triphenolamine (TPA) ligand is reported. Analysis by single-crystal X-ray diffraction and Raman and NMR spectroscopy reveals different coordination geometries for the two titanium centers. Hence, coordination of TPA and a nitrogen ligand results in trigonal-bipyramidal geometry, while an octahedral titanium center is obtained upon additional coordination of an ethoxide generated upon C-O bond cleavage in a diethyl ether solvent molecule. The titanium complex successfully generates ammonia in the presence of an excess amount of PCy3HI and KC8 in 154% yield (per titanium atom). A titanium complex with a bulkier TPA does not form a dinitrogen complex, and mononuclear titanium dinitrogen complexes were not accessible, presumably because of the high tendency of early transition metals to form binuclear dinitrogen complexes.

4,4′-Di-tert-butyl-2,2′-bipyridinium trifluoromethanesulfonate was synthesized by stirring 4,4′-Di-tert-butyl-2,2′-bipyridine with scandium(III) trifluoromethanesulfonate in acetonitrile, followed by precipitation with diethyl ether. The structure of the new compound was characterized by FT-IR, 1H, 13C{1H} and 19F{1H} NMR spectroscopy and CHN elemental analysis. This is a safe and simple method to obtain mono-protonated bipyridinium trifluoromethanesulfonate without the direct use of trifluoromethanesulfonic acid.

The reaction of triphenylantimony with 3,4-dihydroxybenzoic acid in diethyl ether in the presence of hydrogen peroxide afforded a tetranuclear macrocyclic complex, which was characterized by X-ray diffraction data.

Compounds with ordered structures in one or two dimensions are exciting materials and investigated intensively in many different areas of science. Many activities have been put into the preparation of low‐dimensional nano‐scaled structures and many compounds in this size regime are known. Contrary, the number of known compounds that have low‐dimensional macroscopic sized structures that form directly in a chemical reaction is very limited. Here, we present the synthesis of the niobium cluster compound [(Et2O)2H]2[Nb6Cl18], crystals of which grow in form of large hexagonal empty tubes of several centimeter length and diameters in the range of 2 mm. The single‐crystal X‐ray structure of this compound has been refined. Under warming, the compound readily eliminates diethyl ether molecules and decomposes. From a closer look at the crystallization process a step‐by‐step scheme of the procedure of the tube growth is proposed. The overall conclusion from this proposal is that a crucial balance between the cluster solution concentration, the crystal growth speed and the ether diffusion speed results in the formation of macroscopic crystal tubes., Growing tubes: Under appropriate conditions of ether vapor diffusion, the cluster compound [(Et2O)2H]2[Nb6Cl18] forms as macroscopic tubes with millimeter‐size inner diameters.

A novel family of four 1-bromo-2,6-bis{[(λ5-phosphanylidene)imino]methyl}benzene ligands has been synthesized and characterized. The phosphiniminomethyl substituents are decorated with either three phenyl groups, two phenyl and one cyclohexyl group, one phenyl and two cyclohexyl groups, or three cyclohexyl groups. Each ligand was metallated using zero-valent nickel through an oxidative addition to form a family of organonickel(II) complexes, namely (2,6-bis{[(triphenyl-λ5-phosphanylidene)imino]methyl}phenyl-κ3 N,C 1,N′)bromidonickel(II) dichloromethane hemisolvate, [NiBr(C44H37N2P2)]·0.5CH2Cl2, (2,6-bis{[(cyclohexyldiphenyl-λ5-phosphanylidene)imino]methyl}phenyl-κ3 N,C 1,N′)bromidonickel(II) diethyl ether hemisolvate, [NiBr(C44H49N2P2)]·0.5C4H10O, (2,6-bis{[(dicyclohexylphenyl-λ5-phosphanylidene)imino]methyl}phenyl-κ3 N,C 1,N′)bromidonickel(II), [NiBr(C44H61N2P2)], and (2,6-bis{[(tricyclohexyl-λ5-phosphanylidene)imino]methyl}phenyl-κ3 N,C 1,N′)bromidonickel(II), [NiBr(C44H73N2P2)]. This family of complexes represents a useful opportunity to investigate the impact of incrementally changing the steric characteristics of a complex on its structure and reactivity.

A study of the kinetics of ethanol conversion in the presence of Zr-containing zeolites BEA doped with palladium particles has revealed the order of formation of the main reaction products. It has been shown that the primary processes are ethanol dehydrogenation to acetaldehyde on Pd sites and ethanol dehydration to diethyl ether on the acid sites of the catalyst. After that, acetaldehyde undergoes the aldol–croton condensation reaction to form crotonal, which is hydrogenated to butanol on the metal sites. Butanol, in turn, is dehydrated into butenes, which undergo hydrogenation to butane. The presence of hydrogen in the gas phase leads to the displacement of ethanol from the metal surface and prevents the formation of surface carbonates and acetates. It has been found that hydrogen significantly accelerates ethanol dehydration owing to a decrease in the activation energy, which can be attributed to hydrogen spillover to the zeolite. The addition of water inhibits all acid-catalyzed reactions owing to competitive adsorption on acid sites and thereby decreases the butanol yield and the ethanol conversion.

The reactions of tris(p-tolyl)antimony, tris(3-fluorophenyl)antimony, and tris(4-fluorophenyl)antimony with 2-hydroxybenzaldoxime at equimolar amounts in diethyl ether in the presence of hydrogen peroxide have been studied. It has been established that 2-hydroxybenzaldoxime reacts as a bifunctional compound, and the simultaneous oxidation and dearylation of triarylantimony is observed. The products of these reactions are bis(μ3-2-oxybenzaldoximato-O, O′, N)-(μ2-oxo)-tetrakis(p-tolyl)-diantimony (I), -tetrakis(3-fluorophenyl)diantimony (II), and -tetrakis(4-fluorophenyl)diantimony (III), in which two structurally equivalent antimony atoms linked via two tridentate bridging ligands and an oxygen atom have a distorted octahedral coordination with the C2O3N surrounding according to X-ray diffraction study data. Their molecules have three types of Sb–O distances with the bridging oxygen atom (1.942(5), 1.946(5) A in IA and IB, respectively, 1.948(3), 1.953(2) A in II, and 1.954(3), 1.958(3) A in III), the oxygen atoms of oxime groups (2.087(7) A in IA and IB, 2.076(2), 2.097(2) A in II, and 2.094(3), 2.081(3) A in III), and the oxygen atoms of hydroxy groups (2.022(7), 2.024(7) A in IA and IB, respectively, 2.002(3), 2.010(3) A in II, and 2.015(4), 2.019(3) A in III) and Sb⋯N coordination bonds (2.236(8), 2.238(9) A in IA and IB, respectively, 2.256(3), 2.230(3) A in II, and 2.266(4), 2.251(4) A in III).

The catalytic performance of novel water-soluble platinum catalysts modified with various nitrogen-containing and phosphine ligands in the hydrogenation reaction of levulinic acid (LA) into γ-valerolactone (GVL) has been studied in environmentally attractive, green, aqueous monophasic systems. The presence of the Lewis acid aluminum enormously increases the catalytic activity of water-soluble platinum catalysts modified with nitrogen-containing ligands in the LA hydrogenation reaction and high catalytic activities up to 3540 TOF’s per hour with a quantitative selectivity towards GVL have been achieved using Na2PtCl6·6H2O precursors modified with the bidentate bathophenanthrolinedisulfonic acid disodium salt (BPhDS) ligand and low amounts of AlCl3·6H2O promotors (molar ratio of AlCl3·6H2O/Pt = 0.17) in aqueous media. This unprecedented increase in catalytic activity with aluminum promotors for water-soluble transition metal catalytic systems in aqueous-phase hydrogenation reactions has not been described until now in the literature. The apparent activation energy of platinum catalyst modified with the monodentate nitrilotriacetic acid trisodium salt ligand in aqueous medium was calculated and amounts to a relative low value of 73.04 kJ mol−1 when one considers that in the LA hydrogenation reaction this catalyst reduces a less reactive keto group into alcohol functionality. A recycling experiment of the Pt/BPhDS/Al catalyst from the aqueous monophasic LA hydrogenation reaction mixture followed by biphasic recovery of the catalyst in active form from organic reaction products by extraction and simple phase separation of an aqueous/organic two-phase system formed after addition of diethyl ether has shown that the Pt/BPhDS/Al catalyst is stable without loss of activity and selectivity in a consecutive run.

In this study, a hydroxyl-rich Schiff base ligand, H4L, and its resulting complexes with ZnCl2, Zn(CH3COO)2 and Zn(ClO4)2 were explored. Interestingly, depending on the zinc salt and/or the crystallisation method, four unique structures were obtained. A synthesis with ZnCl2 gave 1, a mononuclear structure ((H3L)2Zn), while with Zn(CH3COO)2, a trinuclear system [(H3L)2Zn3(CH3COO)4], 2, was found. Interestingly two multinuclear architectures were observed with Zn(ClO4)2. Firstly, diethyl ether diffusion of a methanolic reaction mixture with minimal atmospheric air volume gave 3, a hexanuclear architecture of the type [(H2L)4(H3L)2Zn6](ClO4)2, while slow evaporation of a similar mixture gave 4, a nonanuclear architecture with the formula [(H2L)6Zn9(CO3)2](ClO4)2. Compound 4 unexpectedly fixed atmospheric CO2 as CO32−, incorporating it into the architecture. As expected, a diethyl ether diffusion with a larger volume of air (∼100 mL) of a similar methanolic reaction mixture gave a mixture of 3 and 4. In addition, bulk samples of all compounds were also investigated by PXRD, and results are in good agreement with the observed single crystal data. Furthermore, complexes 1–4 were characterised using FT-IR and simultaneous thermal analysis (STA), and additionally the photophysical properties of H4L and complexes 1–4 have also been explored.

High catalytic activities (TOF = 3000 h−1) have been achieved by novel water-soluble ruthenium catalysts modified with nitrogen-containing ligands such as the bathophenanthrolinedisulfonic acid disodium salt (BPhDS) in the hydrogenation reaction of the renewable polar platform chemical levulinic acid (LA) which possesses a central relevance in the development of biorefineries of the future in a sustainable way to produce with essentially quantitative selectivity of 99.9 mol% γ-valerolactone (GVL) in aqueous media. The apparent activation energy of the Ru/BPhDS catalyst was calculated and amounts a relative low value of 53.3 kJ/mol when one considers that in the LA hydrogenation reaction this catalyst reduces a less reactive keto group into alcohol functionality. A recycling experiment of the Ru/BPhDS catalyst by extraction after addition of diethyl ether has shown that the catalyst is stable without loss of activity and selectivity in a consecutive run.

Several decades after the bis­(diethyl etherate) of tungsten(IV) chloride was first mentioned in the literature, it has now at last been structurally characterized by single-crystal X-ray diffraction analysis, finally confirming its composition.

The true identity of the diethyl ether adduct of tungsten(IV) chloride, WCl4(Et2O) x , has been in doubt since 1985. Initially postulated as the bis-adduct, WCl4(Et2O)2, questions arose when elemental analyses were more in line with a mono-ether adduct, viz. WCl4(Et2O). It was proposed that this was due to the thermal instability of the bis-adduct. Here, we report the room-temperature X-ray crystal structure and Hirshfeld surface characteristics of trans-tetrachloridobis(diethyl ether)tungsten(IV), trans-WCl4(Et2O)2 or trans-[WCl4(C4H10O)2]. The compound crystallizes, with half of the molecule in the asymmetric unit, in the centrosymmetric space group P21/n. The W—O distance is 2.070 (2) Å, while the W—Cl distances are 2.3586 (10) and 2.3554 (10) Å.

Primary alcohol dehydration reaction catalysis by using γ-Al2O3 catalyst can produce ether compounds and alkenes. The combination chrome-cobalt and alumina catalyst could convert ethanol to diethyl ether in the ethanol dehydration process. The purpose of this study was to determine the performance of Cr-Co with the support of γ-Al2O3 catalyst for ethanol dehydration to diethyl ether. Cr-Co/γ-Al2O3 catalyst was prepared using incipient wetness impregnation. γ-Al2O3 catalyst was impregnated with chrome and cobalt metals at various metal loading 5 and 10% and impregnated ratio of Cr-Co (1:1; 1:2; and 2:1). The samples were calcined at 550°C for 3 hours in nitrogen and then reduced continuously by hydrogen at 600°C for 5 hours. Then catalyst was analyzed for characterization using BET, XRD, and SEM-EDX. Treatment of γ-Al2O3 in various ratio of chrome and cobalt impregnation decreased the total surface area. Increasing metal loading in Cr-Co impregnation on γ-Al2O3 decreased total surface area and increased average pore diameter. Impregnation process lowered the crystallinity but still maintained the material crystal structure. The reduced surface area of the catalyst does not mean the effectiveness of the catalyst is reduced, but the metal will actually increase the active site of the catalyst and will affect the rate of reaction in the catalyst.

Cetirizine as general OTC anti-allergic drug was evaluated through paper chromatography. Twelve cetirizine compositions were analysed wherein each tablet and syrups were six in number. Seven solvent systems were experimented from which chloroform and methanol in ratio 50:50 proved to be best solvent system for both cetirizine tablet and syrup compositions. Other solvent system that showed clear separation of spots were n-hexane, toluene and diethyl ether in ratio 65:25:10 and acetone and methanol in ratio 90:10 for tablet and syrup preparations respectively. Iodine fuming technique and UV radiations were also utilized for visualising some unidentified and invisible spots during the examination procedures.

The synthesis, characterization, and reaction mechanism of a series of oxonium derivatives of the rhenium containing metalladecaborane [nido-6-Re(CO)3B9H13][NMe4] are reported herein. The oxonium species were synthesized using tetrahydrofuran, 1,4-dioxane, and diethyl ether. The crystal structure of the tetrahydrofuran derivative [2-(CH2)4O-nido-6-Re(CO)3B9H12] was determined and compared to the isostructural manganese compound. The title compound crystallizes in the Triclinic space group P-1 with (a = 7.0835(5) A, b = 9.6971(6) A, c = 12.5762(8) A, α = 73.5750(10)o, β = 75.5520(10)o, γ = 87.061(2)o, volume = 802.22(9), Z = 2). This facile functionalization strategy will facilitate future investigations of rhenium containing metallaboranes and metallacarboranes.

The synthesis and crystal structure of 5,10,15,20-tetra­kis α,α,α,α 2-iso­thio­cyanato­phenyl zinc(II) porphyrin are reported. The crystal structure consists of discrete porphyrin complexes that are located on a twofold rotation axis with the ZnII cation in a square-pyramidal coordination environment defined by the porphyrin N atoms at the basal sites and a diethyl ether mol­ecule at the apical site., The crystal structure of the title compound, [Zn(C48H24N8S4)(C4H10O)]·C4H10O, consists of discrete porphyrin complexes that are located on a twofold rotation axis. The ZnII cation is fivefold coordinated by four N atoms of the porphyrin moiety and one O atom of a diethyl ether mol­ecule in a slightly distorted square-pyramidal environment with the diethyl ether mol­ecule in the apical position. The porphyrin backbone is nearly planar with the metal cation slightly shifted out of the plane towards the coordinating diethyl ether mol­ecule. All four iso­thio­cyanato groups of the phenyl substituents at the meso-positions face the same side of the porphyrin, as is characteristic for picket fence porphyrins. In the crystal structure, the discrete porphyrin complexes are arranged in such a way that cavities are formed in which additional diethyl ether solvate mol­ecules are located around a twofold rotation axis. The O atom of the solvent mol­ecule is not positioned exactly on the twofold rotation axis, thus making the whole mol­ecule equally disordered over two symmetry-related positions.

Here, we report on the effect of different antisolvent dripping on film morphology and charge recombination of mixed formamidinium–methylammonium tin iodide (FA0.75MA0.25SnI3) as a light absorber in perovskite solar cells. N,N-dimethyl methanamide (DMF) and dimethyl sulfoxide (DMSO) were used as the mixed solvent in the perovskite precursors together with tin fluoride (SnF2) as an additive. Diethyl ether (DE), toluene (TL), and chlorobenzene (CB) were employed as antisolvents for comparison. Our results show that CB as an antisolvent leads to a dense and uniform Sn-based perovskite film. The maximum power conversion efficiency of our Sn-based perovskite solar cell achieves 9.06% (9.02%) under forward (reverse) voltage scan under AM 1.5G 100 mW/cm2 illumination. The encapsulated cells show good long-term stability with ∼75% of their initial efficiency retained over a period of 30 days of storage. Our work suggests the promising potential to further improve the performance of Pb-free Sn-based perovskite sol...

Liquid-phase hydrogenation of 4-chloronitrobenzene (4-CNB) to 4-chloroaniline (4-CAN) under mild reaction conditions (0.6 MPa, 25 °C, methanol-diethyl ether, 1:1 vol.) over palladium and platinum catalysts containing 1 mass% of metal supported on beta zeolite (M/B) or γ-alumina (M/A) was studied. The catalysts were prepared by the incipient wetness method using amino nitrate complexes and hydrogen as the reducing agent. SEM, adsorption–desorption nitrogen isotherms, XRD, TEM, and hydrogen chemisorption techniques were used for their characterization. The techniques employed revealed the presence of relatively large metal particles (approximately 15 nm; about 3% of metal dispersion). Stability of the catalysts during the hydrogenation was high; no catalyst changes were observed after two recycle runs. Hydrogenation over M/A catalysts was found to be faster than that over M/B catalysts in the methanol–diethyl ether mixture. Selectivity of only about 75% to 4-CAN was achieved over the M/A catalyst in methanol. Positive effect of the acid support (beta zeolite) and low polarity of the reaction environment (diethyl ether) are reflected in the high selectivity to 4-CAN; of about 99% at virtually 100% conversion of 4-CNB.

Thorium(IV) is extracted from chloride medium by solvent extraction using a prepared Schiff base chelating agent, (E)-4-(2-hydroxy phenyl imino) pentane-2-one (AcPh) that is synthesized and characterized by FT-IR, 1H-NMR and elemental analysis. The obtained optimum extraction parameters were 0.02M AcPh/chloroform and diethyl ether ratio mixture, pH 6.5, 3:1 aqueous to organic phase ratio for 5 min. contact time at room temperature. The thorium(IV) was then stripped into aqueous media containing 0.5 M HNO3 solution using of 1:2 aqueous to organic phase ratio for 7 min. contact time at room temperature.

Ozdemir, Namik/0000-0003-3371-9874; DAYAN, Serkan/0000-0003-4171-7297 WOS: 000504781100028 A new Bis[N-(2-aminophenyl)benzenesulfonamidej-di-chloro-Bis[O'-N,N-dimethyl-formamide]-nickel (II) complex [NiCl2(DMF)(2)L2] was synthesized in DMF solution in reflux media with NiCl2.2H(2)O and the pre-prepared N-(2-aminophenyl)benzenesulfonamide and the [NiCl2(DMF)(2)L-2] complex was crystallized in DMF/diethyl ether solution, for its single crystal. The complex characterized by FT-IR, elemental analysis, TG-DTA and UV Vis spectrophotometry methods, and its single crystal study were also performed by X-ray spectroscopy. Additionally, the catalytic efficiency of the fabricated [NiCl2(DMF)(2)L-2] complex was determined by UV Vis spectrophotometry in the reduction reaction of 2-nitroaniline (2-NA), 4-nitroaniline (4-NA) and nitrobenzene (NB) in presence of NaBH4 in water. The best conversion obtained as a result of the reduction of nitroarenes in the short time of 10 min. was 62.5 %, which was obtained at the 2-NA reduction. The conversion obtained from of the reduction of nitroarenes, are sequenced as 2-NA (62.5 %) > NB (56.5 %) > 4-NA (25.5%) in 10 min. In addition, the reaction products, both aqueous and short-term, are harmless to the environment, which will provide a significant reaction variety in terms of green chemistry. (C) 2019 Elsevier Ltd. All rights reserved.