Proton mobility in the solid inorganic hydrates of acids and acid salts

The method for the calculation of the proton-transfer frequency (n_t) and its activation energies (E_t) was suggested. Results of the calculations were presented. The experimental data on the activation energy of proton-containing group rotation and protonconductivity values for some hydrates of inorganic acids and acid salts were compared with the calculated ones.     

Proton NMR Assay of Essential Oils VIII. Assay of Linalool in Coriander Oil

Abstract

A quantitative assay for linalool in a commercial sample of coriander oil is described. Good agreement was obtained with results found by the acetylation method. No interference from other oil constituents was noted.     

Proton dissociation and transfer in hydrated phosphoric acid clusters

The dynamics and mechanisms of proton dissociation and transfer in hydrated phosphoric acid (H₃PO₄) clusters under excess proton conditions were studied based on the concept of presolvation using the H₃PO₄–H₃O⁺–nH₂O complexes (n = 1–3) as the model systems and ab initio calculations and Born–Oppenheimer molecular dynamics (BOMD) simulations at the RIMP2/TZVP level as model calculations. The static results showed that the smallest, most stable intermediate complex for proton dissociation (n = 1) is formed in a low local‐dielectric constant environment (e.g., ε = 1), whereas proton transfer from the first to the second hydration shell is driven by fluctuations in the number of water molecules in a high local‐dielectric constant environment (e.g., ε = 78) through the Zundel complex in a linear H‐bond chain (n = 3). The two‐dimensional potential energy surfaces (2D‐PES) of the intermediate complex (n = 1) suggested three characteristic vibrational and ¹H NMR frequencies associated with a proton moving on the oscillatory shuttling and structural diffusion paths, which can be used to monitor the dynamics of proton dissociation in the H‐bond clusters. The BOMD simulations over the temperature range of 298–430 K validated the proposed proton dissociation and transfer mechanisms by showing that good agreement between the theoretical and experimental data can be achieved with the proposed rate‐determining processes. The theoretical results suggest the roles played by the polar solvent and iterate that insights into the dynamics and mechanisms of proton transfer in the protonated H‐bond clusters can be obtained from intermediate complexes provided that an appropriate presolvation model is selected and that all of the important rate‐determining processes are included in the model calculations. © 2015 Wiley Periodicals, Inc.     

Improved Proton Decoupling in NMR Spectroscopy of Crystalline Solids Using the SPINAL-64 Sequence

Summary.  The performance of three different spin decoupling schemes, CW, TPPM, and SPINAL-64 is compared, by recording proton decoupled ¹³C NMR spectra of a crystalline glycine sample, with 20% isotopic labelling. At a magnetic field of B ₀ = 14.1 T, the two phase modulated pulse schemes, TPPM and SPINAL-64, are shown to give decisively better results than CW decoupling, and the SPINAL-64 sequence is found to perform better than TPPM. It is suggested that in NMR of crystalline solids, SPINAL-64 offers a viable and competitive alternative to the well established TPPM decoupling technique, especially at higher magnetic fields. Corresponding author. E-mail: thomas.braeuniger@durham.ac.uk Received May 6, 2002; accepted May 22, 2002     

Basicity and Proton Transfer in Proton Sponges and Related Compounds: An Ab Initio Study

Theoretical calculations at the B3LYP/6-31G* level were carried out on a family of 1,8-diR-naphthalenes, which include the proton sponge (1,8-bisdimethylaminonaphthalene, R = NMe₂) and other substituents (R = NH₂, R = OH, R = CH₃, R = F). Their basicity was compared with that of the corresponding monosubstituted benzenes. The dianion of 1,8-dihydroxynaphthalene should be a compound of extraordinary high basicity. The barriers to proton transfer, geometry, and density at the bond critical point of the hydrogen bond have been calculated and compared with experimental data when available.     

Synthesis of fluoro-containing sulfonated poly(phthalazinone ether ketone ketone)s and their properties as PEM in PEMFC and DMFC

A series of sulfonated poly(ether ketone ketone)s (SPPFEKKs) containing both of phthalazinone and hexafluoroisopropylidene moieties were synthesized by direct nucleophilic polycondensation reaction from 4-(4-hydroxyphenyl)-1(2H)-phthalazinone (DHPZ), 4,4-hexafluoroisopropylidene-diphenol (BPAF), 1,4-bi(4-fluorobenzoyl) benzene (DFKK) and 1,4-bi(3-sodium sulfonate-4-fluorobenzoyl) benzene (SDFKK). The obtained SPPFEKKs had high molecular weight with inherent viscosity ranged from 1.29 to 1.53 dL/g and their chemical structure was characterized by FT-IR and ¹H NMR. The ionic membranes of SPPFEKKs showed high proton conductivity, for instance, SPPFEKK-120 (DS = 1.20) demonstrated 1.0 × 10⁻¹ S/cm proton conductivity at 95 °C, which was very close to that of Nafion^®117. All the SPPFEKK membranes exhibited methanol permeability lower than 2.76 × 10⁻⁷ cm²/s, which was much lower than that of Nafion^®117 (2.38 × 10⁻⁶ cm²/s). These copolymers also showed excellent thermal stability and good solubility in aprotic polar organic solvents. The ionic membranes of SPPFEKK demonstrated tensile strength varied from 57 to 69 MPa depending on their DS.     

Methanol permeability in sulfonated poly(etheretherketone) membranes: A comparison with Nafion membranes

Partially sulfonated poly(etheretherketone) (SPEEK) samples were prepared by modification of corresponding poly(etheretherketone) (PEEK) with concentrated sulfuric acid. Membranes cast from these materials were evaluated as polymer electrolytes for direct methanol fuel cells (DMFCs). SPEEK membranes were characterized by ¹H NMR, FT-IR and TGA. The transverse proton conductivities increased from 4.1 to 9.3 × 10⁻³ S/cm with the increase of the degree of sulfonation (DS) from 0.59 to 0.93. These values were comparable with that of Nafion 117 membrane (1.0 × 10⁻² S/cm) measured under the same condition. Nearly one order magnitude difference between transverse conductivity and longitudinal conductivity was found. The methanol permeabilities of the SPEEK membranes were all lower than that of Nafion 117 membrane. The effects of temperature and methanol concentration on the methanol permeability were also studied. In addition, the selectivities of the SPEEK membranes for protons and methanol were all higher than that of Nafion 117 membrane.     

Pulsed NMR studies of translational mobility of polymer molecules in polydialkylphosphate gels

The translational mobility of polypropylenephosphate (PPP) molecules has been studied by the NMR pulsed field gradient technique. The translational diffusion of long chain polymer molecules of polymerization degree ¯m > 20 may be neglected, in NMR measurements, on account of their rigidity. The self-diffusion coefficient of short chain polymer molecules (¯m=8) in PPP gels (¯D_s=3 · 10^–8 cm²/s) is about two orders of magnitude lower than that of water molecules in gels.Two hydrates, i. e. PPP(H⁺) · 3H₂O and PPP(H⁺, Mg²⁺) · 5H₂O represent the most stable structures, at temperature 293 K.     

Magnesium doped Gallium Phosphonates Ga1–xMgx[H3+x(O3PCH2)3N] (x = 0, 0.20) and the Influence on Proton Conductivity

In our contribution to the development of new proton conductive coordination polymers (CPs) we focus on the impact of a partial replacement of Ga³⁺ by Mg²⁺. This approach should come along with the introduction of additional protons due to charge balances. In a first step we have synthesized an isostructural compound to the literature known compound AlH₃P3N [H₆P3N = nitrilotris(methylene)triphosphonic acid], where Al³⁺ is replaced by Ga³⁺, since all attempts to incorporate Mg²⁺ ions directly into AlH₃P3N were not successful. The relative amount of Mg²⁺ and Ga³⁺ was established by EDX analysis. Rietveld refinement of the synchrotron data located the Ga³⁺ and Mg²⁺ ions on a split position, proving the disordered incorporation of the Mg²⁺ ions. Solid‐state NMR spectroscopy confirms a disordered protonation of the phosphonate groups as well and shows that all amine groups are protonated. In order to investigate the effect on the proton conductivity the compounds Ga[H₃(O₃PCH₂)₃N], denoted GaH₃P3N as well as Ga_0.80Mg_0.20[H_3.20(O₃PCH₂)₃N], denoted GaMgH_3.20P3N, were characterized by electrochemical impedance spectroscopy (EIS). Arrhenius behavior in the investigated temperature range (70–130 °C) was found for both compounds (activation energies of E_a = 0.15 eV for GaH₃P3N and 0.17 eV for GaMgH_3.20P3N). The GaMgH_3.20P3N sample shows a reduced proton mobility (σ = 1.2 × 10^–4 S · cm^–1) of about one order of magnitude in comparison to GaH₃P3N (σ = 1.0 × 10^–3 S · cm^–1).     

Free‐standing and flexible nano‐ZnO/PVDF composite thin films: impedance spectroscopic studies

Nanocrystalline ZnO‐impregnated polyvinylidene fluoride (nano‐ZnO/PVDF) composite films were prepared by sol‐gel technique. Free‐standing and flexible films with different nano‐ZnO loadings were synthesized. Addition of ZnO in PVDF host matrix modulated the impedance and dielectric properties. The composite films thus obtained were characterized by microstructural, XPS, and impedance spectroscopic measurements. Copyright © 2015 John Wiley & Sons, Ltd.     

Investigation of structural, morphological, luminescent and thermal properties of combusted aluminium-based iron oxide

Nanocomposites of aluminium integrated hematite α-Fe₂O₃ are synthesized by combustion route using aqueous solutions of AR grade ferric trichloride and aluminium nitrate as precursors. The influence of aluminium incorporation on to the morphology, XPS, photoluminescence and thermal properties has been investigated. The FESEM and AFM micrographs depict that the samples are compact and have homogeneously distributed grains of varying sizes (∼20-60 nm). Chemical composition and valence states of constituent elements in hematite are analyzed by XPS. In room temperature photoluminescence (PL) study, we observed strong violet emission around 436 nm without any deep-level emission and a small PL FWHM indicating that the concentrations of defects are responsible for deep-level emissions. The specific heat and thermal conductivity study shows the phonon conduction behavior is dominant. We studied interparticle interactions using complex impedance spectroscopy. We report a new potential candidate for its possible applications in optoelectronics and magnetic devices.     

Investigation of the proton mobility in CsH(SO4)0.76(SeO4)0.24 crystal by H NMR spectroscopy

Crystals of CsH(SO₄)_0.76(SeO₄)_0.24 formulation were studied by ¹H NMR spectroscopy. The ¹H line-shape, the T₁ and T₂ relaxation times were determined as a function of temperature. The activation energies deduced from the temperature dependence of relaxation times were compared with the activation energy issued from conductivity measurements. The results obtained are discussed and supported by the Ngai model.     

Reorientation mobility of NH3-group in glycine crystals by means of H NMR spectroscopy

We report results of ¹H NMR measurements of proton mobility in α-, β-, and γ-polymorphs of glycine, including the energy barriers and specific correlation times for the amino group reorientation process. We discuss relations between second-order phase transition in β-glycine observed at 252 K and proton mobility in β-glycine crystals.     

Electric and dielectric behavior of copper-chromium layered double hydroxide intercalated with dodecyl sulfate anions using impedance spectroscopy

The Cu₂Cr-DS-LDH hybrid was successfully prepared by the anion exchange method at room temperature. The structure, the chemical composition and the physico-chemical properties of the sample were determined using powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and inductively coupled plasma (ICP). In this work, the electrical and dielectric properties investigated are determined using impedance spectroscopy (IS) in a frequency range of 1 Hz to 1 MHz. Indeed, the Nyquist diagram modelized by an electrical equivalent circuit showed three contributions attributed respectively to the polarization of grains, grains boundaries and interface electrode-sample. This modelization allowed us to determine the intrinsic electrical parameters of the hybrid (resistance, pseudo-capacitance and relaxation time). The presence of the non-Debye relaxation phenomena was confirmed by the frequency analysis of impedance. Moreover, the evolution of the alternating current conductivity (σ_ac) studied obeys the double power law of Jonscher. The ionic conduction of this material was generated through a jump movement by translation of the charge carriers. As for the dielectric behavior of the material, the evolution of dielectric constant as a function of frequency shows relatively high values in a frequency range between 10 Hz and 1 KHz. The low values of the loss tangent obtained in this frequency zone can valorize this LDH hybrid.     

Proton diffusion in hybrid materials of CsHSO4 and silica nanoparticles as studied by H solid-state NMR

Hybrid materials of CsHSO₄ and silica nanoparticles were prepared by mechanical milling, and hydrogen bond states and proton dynamics were studied by means of ¹H solid-state NMR. ¹H MAS NMR spectra demonstrated that three types of domains are present in the milled materials. Domain A has hydrogen bond states similar to those in the bulk compound. With respect to hydrogen bonds, domains A-II and A-III are similar to phases II and III of CsHSO₄, respectively. Protons in domain A-II undergo translational diffusion, and the diffusion is faster than in phase II of bulk CsHSO₄. Domain B is originated by mixing of CsHSO₄ with silica nanoparticles, presumably locating at the boundary region. Protons in this domain also undergo translational diffusion. The motional rate is faster than in phase II of bulk CsHSO₄ but is slower than in domain A-II. In domain C protons are contained as OH groups on the surface of silica nanoparticles. Protons are immobile in this domain.     

Investigation of perfluorosulfonic acid ionomer solutions by 19f NMR and DLS: Establishment of an accurate quantification protocol

Long side chain perfluorosulfonic acid (PFSA) aqueous solutions with various degrees of substitution and trifluoroacetic acid solutions were investigated by liquid ¹⁹F nuclear magnetic resonance (NMR) to propose a new and efficient quantification protocol. These two examples were selected to respond to a specific need for quantification in fuel cell applications. Classical quantification revealed a systematic underestimation of the PFSA concentrations at room temperature, in contrast to small fluorinated molecules. Dynamic light scattering data suggested the presence of “NMR silent aggregates” up to 50 °C. These aggregates appeared as large particles of about 30 µm in diameter, resulting from the agglomeration of primary aggregates through hydrogen bonds. An increase of the measurement temperature to 80 °C was sufficient to take apart the secondary aggregates, and get the correct quantification. In parallel, a rapid ¹⁹F NMR quantification method was developed using a careful analysis of the Signal‐to‐Noise ratio. This new method provided, in at least a six decades range, an estimation of the PFSA concentration without the need for an external reference. This approach may be successfully applied to determine the fluorine atom content of any small molecule or polymer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2210–2222     

Proton mobility in hydrates of inorganic acids and acid salts

Published data on the mechanisms of hydrogen ion transport in solids and aqueous solutions are described systematically, including defect formation, rotational mobility of proton-containing groups, proton hopping along a hydrogen bond, proton translational mobility, and proton conduction. Resorting to the authors" theoretical results and published data, the main criteria for the selection of systems possessing high proton mobility are formulated.     

Unusual mobility of hypercrosslinked polystyrene networks: Swelling and dilatometric studies

Hypercrosslinked polystyrene samples were prepared by an intensive postcrosslinking of highly swollen styrene–divinylbenzene copolymer beads to extremely high degrees of crosslinking that amounted to 100% or even higher. When in the dry state, the materials obtained represent transparent beads of reduced density. Despite the high degree of crosslinking, the materials manifest large increases in volume on swelling with any liquid media as well as large changes in volume on heating. The factors determining the unusual swelling ability of the hypercrosslinked polymers are briefly discussed. Thermodilatometric tests of the polymers with a moderate degree of crosslinking reveal a certain contraction of the beads at temperatures higher than 100 °C. When crosslinked far beyond 100%, the networks demonstrate unusual expansion in the 100–220 °C range; this is followed by a sharp shrinking at higher temperatures. The former is caused by an increased intensity of the vibration movements of the network and a partial relaxation of strong inner stresses; the latter is due to partial chemical oxidation, degradation of network units, or both. This degradation, however, is not accompanied by any loss in weight of the polymer but only results in a transformation into a more dense conventional nonporous material. The strained, rigid open‐work structure of the homogeneous expanded hypercrosslinked polystyrene networks is responsible for their unusual mobility. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1553–1563, 2000     

Proton shuttle efficiency of bicarbonate: A theoretical study on tautomerization and CO2 hydration

The efficiency of bicarbonate molecule (HCO₃⁻) as a proton shuttle in the tautomerization and (non)enzymatic CO₂ hydration reactions has been investigated with the aid of computational chemistry methods (DFT and ab initio). The results revealed that bicarbonate can decrease the barrier height of tautomerization (keto-enol, azo-hydrazo and imine-amine) more than 70%. This value is around 45% for water molecules. Also, HCO₃⁻ can catalyze the CO₂ hydration both inside (enzymatic) and outside (nonenzymatic) the active site of human carbonic anhydrases II (HCA II). In the absence of enzyme, bicarbonate molecule can lower the CO₂ hydration from ∼50 kcal mol⁻¹ in the gas phase to ∼14 kcal mol⁻¹ in the aqueous media. This reaction maintains its barrier (∼15 kcal mol⁻¹) for bicarbonate-Zn complex in the active site of enzyme; it has been observed that amino acid residues, mainly Thr199 and Glu106, are actively involved in the proton transfer network and facilitate CO₂ hydration ability of bicarbonate.     

Surface chemistry of selected supported metallocene catalysts studied by DR‐FTIR,CPMAS NMR,and XPS techniques

Two supported metallocene catalysts (CS 1: PQ 3030/MAO/Cp₂ZrCl₂ and CS 2: PQ 3030‐BuGeCl₃/MAO/Cp₂ ZrCl₂) were prepared by sequentially loading MAO and Cp₂ZrCl₂ on partially dehydroxylated silica PQ 3030. In catalyst CS 2, ⁿBuGeCl₃ was used to functionalize the silica. These catalysts were characterized by DR‐FTIR spectroscopy, CPMAS NMR spectroscopy, and XPS. Their catalytic performance was evaluated by polymerizing ethylene using the MAO cocatalyst and characterizing the resulting polymers by GPC. Both catalysts produced two metallocenium cations (Cation 1: [Cp₂ZrCl]⁺ and Cation 2: [Cp₂ZrMe]⁺) with comparable equilibrium concentrations and showed varying solid‐state electronic environments. The modified supports (PQ 3030/MAO and PQ 3030‐BuGeCl₃/MAO) acted as weakly coordinating polyanions and stabilized the above cations. BuGeCl₃ did not affect the solid‐state electronic environment. However, it increased the surface cocatalyst to catalyst molar ratio (Al:Zr), acted as a spacer, increased catalyst activity, and enhanced chain‐transfer reactions. The separately fed MAO cocatalyst shifted the equilibrium between Cation 1 and Cation 2 toward the right. Consequently, more Cation 2 was generated, which acted as the effective and active single‐site catalytic species producing monomodal PDI. Copyright © 2006 John Wiley & Sons, Ltd.