0000000000214303
AUTHOR
Abel García-bernabé
Synthesis and X-ray Crystallographic Characterization of (μ-(Diphenylphosphino)phenyl-C2,P)palladium Bromide. A Novel Tetranuclear Metalated Compound
The synthesis and crystal structure of a tetranuclear palladium cluster, [Pd(PC)Br]4 (PC) = [P(C6H4)Ph2]-), is described. Cleavage of this cluster with phosphines yields the mononuclear species Pd(PC)Br(P) in the form of cis and trans isomers. An equilibrium between mono- and tetranuclear species is observed for P = PCBr.
Proton conductivity through polybenzimidazole composite membranes containing silica nanofiber mats
The quest for sustainable and more efficient energy-converting devices has been the focus of researchers&prime
A Deep Insight into Different Acidic Additives as Doping Agents for Enhancing Proton Conductivity on Polybenzimidazole Membranes
[EN] The use of phosphoric acid doped polybenzimidazole (PBI) membranes for fuel cell applications has been extensively studied in the past decades. In this article, we present a systematic study of the physicochemical properties and proton conductivity of PBI membranes doped with the commonly used phosphoric acid at different concentrations (0.1, 1, and 14 M), and with other alternative acids such as phytic acid (0.075 M) and phosphotungstic acid (HPW, 0.1 M). The use of these three acids was reflected in the formation of channels in the polymeric network as observed by cross-section SEM images. The acid doping enhanced proton conductivity of PBI membranes and, after doping, these conducti…
Effect of metallacarborane salt H[COSANE] doping on the performance properties of polybenzimidazole membranes for high temperature PEMFCs
[EN] In this paper, a series of composite proton exchange membranes comprising a cobaltacarborane protonated H[Co(C2B9H11)(2)] named (H[COSANE]) and polybenzimidazole (PBI) for a high temperature proton exchange membrane fuel cell (PEMFC) is reported, with the aim of enhancing the proton conductivity of PBI membranes doped with phosphoric acid. The effects of the anion [Co(C2B9H11)(2)] concentration in three different polymeric matrices based on the PBI structure, poly(2,2 '-(m-phenylene)-5,5 '-bibenzimidazole) (PBI-1), poly[2,2 '-(p-oxydiphenylene)-5,5 '-bibenzimidazole] (PBI-2) and poly(2,2 '-(p-hexafluoroisopropylidene)-5,5 '-bibenzimidazole) (PBI-3), have been investigated. The conducti…
Photo-assisted formation of a chelating diphos ligand from PPh3 and a cyclometallated [P(C6H4)(C6H5)2]− ligand. Crystal structure of Pd{η2-o-[P(C6H5)2]2(C6H4)}Br2
Abstract The cyclometallated palladium compound, Pd[η2-(C6H4)P(C6H5)2]Br[P(C6H5)3] (1), in the solid state by action of light, evolves to give Pd{η2-o-[P(C6H5)2]2(C6H4)}Br2 (2). This compound contains the diphosphine, o-[P(C6H5)2]2(C6H4), as chelated ligand that is formed by a couple reaction of the metallated ligand η2-[(C6H4)P(C6H5)2]− and the coordinated arylphosphine. A study by NMR spectroscopy confirms that the o-phenylene bridge in the diphosphine ligand in 2 comes from the metallated phosphine ligand in 1.
Influence of the anion on diffusivity and mobility of ionic liquids composite polybenzimidazol membranes
[EN] The study of proton conductivity processes has received increasing attention in the past decades due to their potential applications in fields such as electrochemical devices and fuel cells. Despite the high number of composite membranes which have been described for this purpose, fundamental studies of the conduction phenomena in polymeric membranes are scarce. In this article, we study on the effect of the anion on ionic conductivity of ionic liquid composite polybenzimidazole (PBI) membranes. These membranes, which contain 1-butyl-3-methylimidazolium (BMIM) with different counterions ([Cl]-, [NCS]-, [NTf2]- and [BF4]-) were analyzed by electrochemical impedance spectroscopy (EIS) in…
Synthesis, Reactivity, and X-ray Crystallographic Characterization of Mono-, Di-, and Tetranuclear Palladium(II)-Metalated Species
The reactivity of the tetranuclear metallated palladium compound (Pd[mu 2-(C6H4)PPh2]Br)4 (1) with different ligands has been investigated with the aim of evaluating the influence of the entering ligand on the nature of the reaction products. The results confirmed the ability of the ligand [(C6H4)PPh2]- to expand a bridging [mu 2-] or a chelating [eta 2-] coordination mode, depending on the auxiliary ligands present in the complex. Bulky phosphines stabilize mononuclear species of formula (Pd[eta 2-(C6H4)PPh2]Br[P]), with a four-atom metallocycle, while small phosphines give dinuclear compounds. The molecular structures of three different metalated palladium compounds have been determined b…
Ionic Liquid Composite Polybenzimidazol Membranes for High Temperature PEMFC Applications
A series of proton exchange membranes based on polybenzimidazole (PBI) were prepared using the low cost ionic liquids (ILs) derived from 1-butyl-3-methylimidazolium (BMIM) bearing different anions as conductive fillers in the polymeric matrix with the aim of enhancing the proton conductivity of PBI membranes. The composite membranes prepared by casting method (containing 5 wt. % of IL) exhibited good thermal, dimensional, mechanical, and oxidative stability for fuel cell applications. The effects of anion, temperature on the proton conductivity of phosphoric acid-doped membranes were systematically investigated by electrochemical impedance spectroscopy. The PBI composite membranes containin…
Diffusivity and free anion concentration of ionic liquid composite polybenzimidazole membranes.
[EN] In this article, PBI composite membranes containing the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM-NTf2) at 1, 5, 10, 20 and 50 wt% (named PBI-IL-x) have been prepared by a casting method. The internal morphology of the membranes was analyzed by scanning electron microscopy (SEM), revealing that the incorporation of IL promotes the formation of porous channels. Thermal and mechanical stability was confirmed by thermogravimetric analysis (TGA) and tensile test measurements. The ionic transport through membranes was analysed by means of electrochemical impedance spectroscopy (EIS), showing a dependence on the IL loading, reaching a highest condu…
Phosphoric Acid Doped Polybenzimidazole (PBI)/Zeolitic Imidazolate Framework Composite Membranes with Significantly Enhanced Proton Conductivity under Low Humidity Conditions
The preparation and characterization of composite polybenzimidazole (PBI) membranes containing zeolitic imidazolate framework 8 (ZIF-8) and zeolitic imidazolate framework 67 (ZIF-67) is reported. The phosphoric acid doped composite membranes display proton conductivity values that increase with increasing temperatures, maintaining their conductivity under anhydrous conditions. The addition of ZIF to the polymeric matrix enhances proton transport relative to the values observed for PBI and ZIFs alone. For example, the proton conductivity of PBI@ZIF-8 reaches 3.1 10&minus
Proton Conducting Electrospun Sulfonated Polyether Ether Ketone-Graphene Oxide Composite Membranes
[EN] A series of novel composite membranes, based on sulfonated poly(ether ketone) (SPEEK) with a graphene oxide (GO) layer, were prepared. One contained a GO layer sandwiched between the SPEEK-polyvinyl alcohol (PVA) matrix (SPEEK/PVA@GO), and another deposited thin layers of GO on the nanofibers of SPEEK-polyvinyl butyral (PVB), with both sandwiched in the phase matrix of SPEEK-PVA (SPEEK/PVA@GO-NF). Various nanofiber thicknesses were studied by varying the electrospinning time. The prepared composite membranes with different nanofiber thicknesses were characterized by scanning electron microscopy, water uptake, ionic exchange capacity, thermogravimetric analysis, mechanical properties an…
Photochemical ligand rearrangement in dirhodium(II) compounds. Structure of Rh2(O2CCH3)2(η2-O2CCH3)[(C6H4)PPh2] (η2-PCCl)(PCClP-ClC6H4)Ph2
Abstract The photochemical reaction of the adducts Rh2(O2CCH3)3[(C6H4)P(o-ClC6H4)Ph]· (P(p-XC6H4)3) (X=H, Me, Cl), yield the compounds Rh2(O2CCH3)2(η2-O2CCH3)[(p-XC6H3)P (p-XC6H4)2](η2-PCCl), (PCCl=P(o-ClC6H4)Ph2) in a ligand rearrangement reaction that involves activation of CH and RhC bonds. The factors that favour this process are studied by carrying out photochemical reactions with different phosphines. The structures of Rh2(O2CCH3)2(η2-O2CCH3) [(C6H4)PPh2](η2-PCCl) has been determined by X-ray diffraction. Mr=1321.1, orthorhombic, space group Pbcn, a=20.339(8), b=20.07(6), c=23.07(3) A , V=9413(3) A 3 , Z=8, D x =1.86 g cm −3 . Mo Kα radiation (graphite crystal monochromator, λ=0.071…