Phosphonic Acid Functional Groups Research Articles

Understanding and exploiting interfacial interactions between phosphonic acid functional groups and co-evaporated perovskites

Understanding and exploiting interfacial interactions between phosphonic acid functional groups and co-evaporated perovskites

Selective recovery of europium from real acid mine drainage by using novel amine based modified SBA15 adsorbent and membrane distillation system

Recovery of rare earth elements (REE) from secondary waste streams promises numerous advantages. Europium (Eu) is an essential component in various high-tech applications, including clean energy technologies. Ensuring a stable supply of europium through recycling reduces the vulnerability to supply disruptions and price fluctuations in the global market. To achieve this, there is a need for development of highly selective and commercially viable adsorbents for Eu recovery. This research presents a novel material, SBA15-NH-PMIDA, synthesized through a two-step surface modification process for selective retrieval of Eu from real acid mine drainage (AMD). Initially, comprehensive physical and chemical characterizations of the material were conducted to confirm its successful synthesis. Subsequent single-solute Eu adsorption experiments demonstrated that SBA15-NH-PMIDA achieved equilibrium within 2 h and exhibited a maximum Langmuir adsorption capacity of 86.21 mg/g at optimal pH of 4.8. It exhibited remarkable selectivity in recovering over 80 % of Eu from pH-adjusted real AMD, with an optimal dosage of 0.8 g/L. Next, a hybrid system amalgamating Direct Contact Membrane Distillation (DCMD) and adsorption was devised. This hybrid system involved the suspension of granulated SBA15-NH-PMIDA within the feed tank to treat pH-adjusted AMD. The DCMD system achieved an 80 % recovery of purified water while concentrating Eu ions by more than threefold, facilitating efficient and selective Eu recovery surpassing 90 %. Importantly, the uptake of other competing metals remained below 10 %. This is attributed to the formation of Eu complexes with phosphonic and carboxyl acid functional groups. SBA15-NH-PMIDA demonstrated its sustainability and viability by consistently retaining over 90 % of its adsorption capacity throughout ten regeneration cycles.

Synthesis, characterization, photo-polymerization, hydrolytic stability, and etching behavior of new self-etch adhesive monomers

Considering the poor hydrolytic stability of the most methacrylate-based functional monomers of self-etch dental adhesives in acidic and aqueous conditions, in this study allyl-based photo-polymerizable self-etch monomers was synthesized in order to improve the hydrolytic stability.The new self-etch monomers based on phosphonic acid functional groups were synthesized through a two-step procedure. First, phosphoric anhydride, poly-phosphoric acid, and polyethylene glycol were reacted to produce phosphate ester precursor (P-PEG-P). Next, allyl 2, 3-epoxypropyl ether was reacted with P-PEG-P to synthesize allyl self-etch monomer. Glycidyl methacrylate was also reacted with P-PEG-P to synthesize a methacrylate self-etch analogue monomer. The monomers were characterized using FTIR and 1H-NMR spectroscopy. The viscosities of monomers were measured using a rheometer. The degree photopolymerization conversion of monomers was measured using FTIR spectroscopy. The pH assay was performed by a digital pH-meter. The etching behavior of the monomers on human teeth was studied using scanning electron microscopy (SEM). Thermo-gravimetric analysis (TGA) was performed to evaluate the possible interaction of the monomers with tricalcium phosphate (TCP). The solubility of synthesized monomers was examined in ethanol, acetone, and water. The hydrolytic stability of cured resins in artificial saliva during 4 months was also surveyed.The synthesis of new self-etching monomers was successfully confirmed by spectroscopy analyses. The results represented appropriate viscosity of self-etching monomers around 1 (Pa s). The resin containing methacrylate monomer exhibited its degree of conversion is more than that of allyl monomer (p < 0.05). The allyl and methacrylate self-etch monomers exhibited pH values of 1.2 and 1.3, respectively. SEM micrograph verified that the synthesized monomers were able to suitable etching of the enamel human premolar teeth. The data obtained from TGA tests revealed that thermal stability of (TCP) containing monomers is enhanced. Also, the monomers exhibited an excellent solubility in polar solvents, but when they are mixed with TCP, they are not, anymore, dissolved in these solvents. Furthermore, the allyl monomer showed higher hydrolytic stability than the methacrylate monomer.The new photo-polymerizable acidic monomer based on allyl functionality showed enhanced hydrolytic stability compared to methacrylate-based monomer. It may be considered as a promising monomer for self-etch dental adhesives.

Selective separation and recovery of vanadium from acid leaching solution of polymetallic black shale as function of aminophosphonic acid

AbstractBACKGROUNDAcid leaching is an effective method to extract vanadium from polymetallic black shale. However, a large amount of metal impurities, especially iron and aluminum, which accompany V, are released during this process.RESULTSIn this study, a aminophosphonic acid chelating resin was used for the differential adsorption and desorption of vanadium, iron and aluminum ions to achieve deep separation and concentration of vanadium ions present in the acid leaching solution of polymetallic black shale. Results showed that vanadium adsorption efficiency reached 90.17% at a pH of 1.8. After differential adsorption and desorption, the V:Fe and V:Al concentration ratios increased from 1.84 to 64.53 and from 0.24 to 37.92, respectively. When a 2.5 mol L−1 NaOH solution was used as desorbent, the separation factors β(V/Fe) and β(V/Al) reached values of 694.22 and 452.29, realizing the selective separation and concentration of vanadium.CONCLUSIONIt was found that the vanadium, iron and aluminum ions were selectively adsorbed onto the phosphonic acid functional groups (PO(OH)2) and amino functional groups (NH). The vanadium ions existed in the form of the polyvanadate (), which can be directionally adsorbed onto PO(OH)2 under POH bond cleavage and coordination of to the unsaturated phosphorus atom and then desorbed through the exchange between hydroxide anions OH− and . The iron and aluminum ions cannot be desorbed by OH− because the iron and aluminum sulfate moieties and were capable of coordinating to the nitrogen atom of the NH group via its lone electron pair. © 2022 Society of Chemical Industry (SCI).

Synergistically integrated phosphonated poly(pentafluorostyrene) for fuel cells.

Modern electrochemical energy conversion devices require more advanced proton conductors for their broad applications. Phosphonated polymers have been proposed as anhydrous proton conductors for fuel cells. However, the anhydride formation of phosphonic acid functional groups lowers proton conductivity and this prevents the use of phosphonated polymers in fuel cell applications. Here, we report a poly(2,3,5,6-tetrafluorostyrene-4-phosphonic acid) that does not undergo anhydride formation and thus maintains protonic conductivity above 200 °C. We use the phosphonated polymer in fuel cell electrodes with an ion-pair coordinated membrane in a membrane electrode assembly. This synergistically integrated fuel cell reached peak power densities of 1,130 mW cm-2 at 160 °C and 1,740 mW cm-2 at 240 °C under H2/O2 conditions, substantially outperforming polybenzimidazole- and metal phosphate-based fuel cells. Our result indicates a pathway towards using phosphonated polymers in high-performance fuel cells under hot and dry operating conditions.

Molecular dynamics simulations of the binging affinity of 1-hydroxyethane-1, 1-diphosphonic acid (HEDP) with nano-hydroxyapatite and the uptake of Cu2+ by HEDP-HAP hybrid systems

The adsorption capacities of different ratios of 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP) and nano-hydroxyapatite (HAP) hybrid systems on Cu2+ were probed. The FTIR, XRD, SEM and EDS analyses showed that HEDP with Cu2+ adsorbed on the surface of HAP and a new crystal phase appeared. The content of adsorbed Cu2+ were 4.4% and 21.8% on the surface of single HAP and HEDP-HAP-0.5 hybrid system, respectively, and later was 4.94 times that of the former. Conversely, the Ca/P (mol) ratio decreased from 1.40 to 0.61, indicating more Ca2+ were replaced by Cu2+. Meanwhile, molecular dynamics (MD) simulations results showed that HEDP and water molecules both formed ordered adsorption layer with similar concentration profiles, but the former preferred to gather on the HAP surface than the latter. The electrovalence bonds between the phosphonic acid functional groups of HEDP and Ca2＋ of HAP surface played the dominant role in their adsorption. The adsorption results showed that the maximum adsorption capacity of single hydroxyapatite for Cu2+ was 40.32 mg/g, while the maximum adsorption capacities reached 99.11, 171.8 and 147.27 mg/g for HEDP-HAP-0.2, HEDP-HAP-0.5 and HEDP-HAP-1.0 hybrid systems, respectively. The study illustrated that the adsorption process accorded with the pseudo-second-order kinetic and Langmuir isotherm model.

Phosphonated mesoporous silica based composite membranes for high temperature proton exchange membrane fuel cells

Mesoporous Santa Barbara Amorphous (SBA-15) was synthesized, and it was grafted with phosphonate functionality using a simple two-step process involving chloromethylation and subsequent phosphonation. The phosphonated SBA-15 (PSBA-15) was characterized using Fourier transform infra-red (FTIR) spectroscopy, solid-state 13C nuclear magnetic resonance (NMR), 29Si NMR, and 31P NMR for confirming successful modification. Morphology features were verified by small angle X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy TEM analyses. Poly(styrene-ethylene-butylene-styrene) (PSEBS) was chosen as the base polymer and phosphonic acid functional groups were grafted onto the polymer using the aforementioned approach, where chloromethyl (-CH2Cl) groups were attached to the main chain using Friedel Craft’s alkylation, followed by the phosphonation of the chloromethylated polymer by the Michaels-Arbuzov reaction resulting in phosphonated PSEBS (PPSEBS). The functionalization was confirmed using NMR and FTIR spectroscopy studies. Composite PPSEBS/PSBA-15 membranes were fabricated with different filler concentrations (2, 4, 6, and 8%) of PSBA-15. Various studies such as water uptake, ion exchange capacity, and the proton conductivity of the composite membranes were undertaken with respect to fuel cell applications. From the studies, it was found that the PPSEBS/PSBA-15 membrane with 6 wt% of filler exhibited maximum proton conductivity of 8.62 mS/cm at 140 °C. Finally, membrane electrode assembly (MEA) was fabricated using PPSEBS/6% PSBA composite membrane, platinium (Pt) anode, and Pt cathode, and was tested in an in-house built fuel cell setup. A maximum power density of 226 mW/cm2 and an open circuit voltage of 0.89 V were achieved at 140 °C under un-humidified condition.

Synthesis and Evaluation of New Bifunctional Chelators with Phosphonic Acid Arms for Gallium-68 Based PET Imaging in Melanoma.

Due to the increasing use of generator-produced radiometal Gallium-68 (68Ga) in positron-emission tomography/computed tomography (PET/CT), reliable bifunctional chelators that can efficiently incorporate 68Ga3+ into biomolecules are highly desirable. In this study, we synthesized two new bifunctional chelators bearing one or two phosphonic acid functional groups, named p-SCN-PhPr-NE2A1P and p-SCN-PhPr-NE2P1A, with the aim of enabling facile production of 68Ga-based radiopharmaceuticals. Both chelators were successfully conjugated to LLP2A-PEG4, a very late antigen-4 (VLA-4) targeting peptidomimetic ligand, to evaluate their application in 68Ga-based PET imaging. NE2P1A-PEG4-LLP2A exhibited the highest 68Ga3+ binding ability with molar activity of 37 MBq/nmol under mild temperature and neutral pH. Excellent serum stability of 68Ga-NE2P1A-PEG4-LLP2A was observed, which was consistent with the result obtained from density functional theory calculation. The in vitro cell study showed that 68Ga-NE2P1A-PEG4-LLP2A had significantly longer retention in B16F10 cells comparing to the reported retention of 64Cu-NE3TA-PEG4-LLP2A, although the uptake was relatively lower. In the biodistribution and micro-PET/CT imaging studies, high tumor uptake and low background were observed after 68Ga-NE2P1A-PEG4-LLP2A was injected into mice bearing B16F10 tumor xenografts, making it a highly promising radiotracer for noninvasive imaging of VLA-4 receptors overexpressed in melanoma.

Dynamics of proton exchange in a model phosphonic acid-functionalized polymer

The dynamics and mechanism of proton exchange in phosphonic acid-functionalized polymers were studied using poly(vinyl-phosphonic acid) (PVPA) as a model system along with quantum chemical calculations and Born–Oppenheimer molecular dynamics (BOMD) simulations at the B3LYP/TZVP level as model calculations. This theoretical study began with searching for the smallest, most active polymer segments and their intermediate conformations which could be involved in the local proton-exchange process. The B3LYP/TZVP results confirmed that a low local dielectric environment and excess proton conditions are required to generate the intermediate conformations, and the shapes of the potential energy curves of the proton exchange between the two phosphonic acid functional groups are sensitive to the local conformational changes. In contrast, a high local dielectric environment increases the energy barriers, thereby preventing the proton from returning to the original functional group. Based on the static results, a mechanism for the proton exchange between the two functional groups involving fluctuations in the local dielectric environment and a local conformational change was proposed. The BOMD results confirmed the proposed mechanism by showing that the activation energies for the proton exchange in the hydrogen bond between two immobilized phosphonic acid moieties, obtained from the exponential relaxation behaviors of the envelopes of the velocity autocorrelation functions and the 1H Nuclear Magnetic Resonance (NMR) line-shape analyses, are too low to be the rate-determining process. Instead, coupled librational motion in the backbone which leads to the interconversion between the two intermediate conformations possesses higher activation energy, and therefore represents one of the most important rate-determining processes. These findings suggested that the rate of the proton exchange in the model phosphonic acid-functionalized polymer is determined by the polymer mobility which, in this case, is the large-amplitude librational motion of the vinyl backbone. © 2015 Wiley Periodicals, Inc.

Silver-based hybrid materials from meta- or para-phosphonobenzoic acid: influence of the topology on silver release in water.

Three novel silver-based metal-organic frameworks materials, which were synthesized from either 3-phosphono or 4-phosphonobenzoic acid and silver nitrate, are reported. The novel hybrids were synthesized under hydrothermal conditions; the pH of the reaction media was controlled by adding different quantities of urea thereby producing different topologies. Compound 1 (Ag3(4-PO3-C6H4-COO)), synthesized in the presence of urea, exhibits a compact 3D structure in which both phosphonic acid and carboxylic acid functional groups are linked to the silver-based inorganic network. Compound 2 (Ag(4-PO3H-C6H4-COOH)), which was synthesized at lower pH (without urea), has a layered structure in which only the phosphonic acid functional groups from 4-phosphonobenzoic acid moieties are linked to the silver inorganic network; the carboxylic acid groups being engaged in hydrogen bonds. Finally, material 3 (Ag(3-PO3H-C6H4-COOH)) was synthesized from 3-phosphonobenzoic acid and silver nitrate without urea. This material 3 features a layered structure exhibiting carboxylic acid functional groups linked via hydrogen bonds in the interlayer space. After the full characterization of these materials (single X-ray structure, IR, TGA), their ability to release silver salts in aqueous environment was measured. Silver release, determined in aqueous solution by cathodic stripping voltammetry, shows that the silver release capacity of these materials is dependent on the topology of the hybrids. The more compact structure 1 is extremely stable in water with only trace levels of silver ions being detected. On the other hand, compounds 2 and 3, in which only the phosphonic acid functional groups were bonded to the inorganic network, released larger quantities of silver ions into aqueous solution. These results which were compared with the silver release of the previously described compound 4 (Ag6(3-PO3-C6H4-COO)2). The results clearly show that the release capacity of silver-based metal organic framework can be tuned by modifying their topology which, in the present study, is governed by the regio-isomer of the organic precursor and the synthetic conditions under which the hybrids are prepared.

Comparison of silatrane, phosphonic acid, and carboxylic acid functional groups for attachment of porphyrin sensitizers to TiO2 in photoelectrochemical cells

A tetra-arylporphyrin dye was functionalized with three different anchoring groups used to attach molecules to metal oxide surfaces. The physical, photophysical and electrochemical properties of the derivatized porphyrins were studied, and the dyes were then linked to mesoporous TiO2. The anchoring groups were β-vinyl groups bearing either a carboxylate, a phosphonate or a siloxy moiety. The siloxy linkages were made by treatment of the metal oxide with a silatrane derivative of the porphyrin. The surface binding and lability of the anchored molecules were studied, and dye performance was compared in a dye-sensitized solar cell (DSSC). Transient absorption spectroscopy was used to study charge recombination processes. At comparable surface concentration, the porphyrin showed comparable performance in the DSSC, regardless of the linker. However, the total surface coverage achievable with the carboxylate was about twice that obtainable with the other two linkers, and this led to higher current densities for the carboxylate DSSC. On the other hand, the carboxylate-linked dyes were readily leached from the metal oxide surface under alkaline conditions. The phosphonates were considerably less labile, and the siloxy-linked porphyrins were most resistant to leaching from the surface. The use of silatrane proved to be a practical and convenient way to introduce the siloxy linkages, which can confer greatly increased stability on dye-sensitized electrodes with photoelectrochemical performance comparable to that of the other linkers.

Molecular Adsorption on ZnO(101̅0) Single-Crystal Surfaces: Morphology and Charge Transfer

While ZnO has excellent electrical properties, it has not been widely used for dye-sensitized solar cells, in part because ZnO is chemically less stable than widely used TiO(2). The functional groups typically used for surface passivation and for attaching dye molecules either bind weakly or etch the ZnO surface. We have compared the formation of molecular layers from alkane molecules with terminal carboxylic acid, alcohol, amine, phosphonic acid, or thiol functional groups on single-crystal zinc oxide (1010) surfaces. Atomic force microscopy (AFM) images show that alkyl carboxylic acids etch the surface whereas alkyl amine and alkyl alcohols bind only weakly on the ZnO(1010) surface. Phosphonic acid-terminated molecules were found to bind to the surface in a heterogeneous manner, forming clusters of molecules. Alkanethiols were found to bind to the surface, forming highly uniform monolayers with some etching detected after long immersion times in an alkanethiol solution. Monolayers of hexadecylphosphonic acid and octadecanethiol were further analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. AFM scratching shows that thiols were bound strongly to the ZnO surface, suggesting the formation of strong Zn-S covalent bonds. Surprisingly, the tridentate phosphonic acids adhered much more weakly than the monodentate thiol. The influence of organic grafting on the charge transfer to ZnO was studied by time-resolved surface photovoltage measurements and electrochemical impedance measurements. Our results show that the grafting of thiols to ZnO leads to robust surfaces and reduces the surface band bending due to midgap surface states.

Rigid Aryl-Phosphonic Acids: Building Blocks for Hybrid Materials

Rigid organic building blocks possessing both phosphonic acid and carboxylic acid functional groups have been used to produce original metal organic frameworks materials.

Modeling of Iron Removal from Spent Passivation Baths by Ion Exchange in Fixed-Bed Operation

In this work the mathematical model that describes the kinetics of the fixed-bed ion exchange iron separation from chromium(III) passivating baths is presented. Passivation is a common step in the zinc electrodeposition galvanic process. The removal of iron species from the passivation baths allows the extention of their life, thus reducing the amount of waste to be managed and the consumption of raw materials. A commercial chelating resin, Purolite S-957, containing sulfonic and phosphonic acid functional groups was employed. Equilibrium experiments, carried out under isothermal conditions at 20 °C, were correlated to the Freundlich equation, with the following parameters KF ) 25 700((mg (n-1)/n L 1/n )/kgdry_resin) and n ) 2.45. A simple mathematical model assuming a reversible chemical reaction as the rate-controlling step has been developed to describe the fixed-bed iron removal rate in the media solutions under study. The value of the unknown parameter, the rate coefficient for the forward reaction, kd ) 10 660[(mg (n-1)/n L 1/n )/(kgdry_resin h)] was obtained from experimental data of iron uptake employing parameter estimation software. The proposed model offers a satisfactory description of the behavior of the iron loading curves for three different types of real passivation baths under variable feed iron concentration and loading flow rate, using only one estimated parameter.

Synthesis and evaluation of new dental monomers with both phosphonic and carboxylic acid functional groups

AbstractNovel dental monomers containing both phosphonic and carboxylic acid functional groups were prepared. The monomers were based on t‐butyl α‐bromomethacrylate (t‐BuBMA) and synthesized in three steps: The reaction of o‐hydroxyaryl phosphonates [diethyl (2‐hydroxyphenyl) phosphonate, tetraethyl (2,5‐dihydroxy‐1,4‐phenylene) diphosphonate and tetraethyl 5,5′‐(propane‐2,2‐diyl)bis(2‐hydroxy‐5,1‐ phenylene) diphosphonate] with t‐BuBMA, the hydrolysis of phosphonate groups to phosphonic acid using trimethyl silylbromide, and the hydrolysis of the t‐butyl groups to carboxylic acid with trifluoroacetic acid. The monomers were solids and soluble in water and ethanol. The structures of the monomers were determined by Fourier transform infrared (FTIR), 1H, 13C, and 31P nuclear magnetic resonance (NMR) spectroscopy. The copolymerization behaviors of the synthesized monomers with glycerol dimethacrylate were first investigated in bulk using photodifferential scanning calorimetry at 40 °C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as photoinitiator. Then, the solution copolymerization of the monomers with acrylamide in ethanol and water was studied, indicating that the synthesized monomers are incorporated into the copolymers. The acidic nature of the aqueous solutions of these monomers (pH values 1.72–1.87) is expected to give them etching properties important for dental applications. The interaction of the monomers with hydroxyapatite was investigated using 13C NMR and FTIR techniques. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1953–1965, 2009

Phosphonic acid grafted bis(4-γ-aminopropyldiethoxysilylphenyl)sulfone (APDSPS)-poly(vinyl alcohol) cross-linked polyelectrolyte membrane impervious to methanol

A new monomer precursor, bis(4-γ-aminopropyldiethoxysilylphenyl)sulfone (APDSPS), has been synthesized and cross-linked poly(vinyl alcohol) (PVA)-APDSPS composite polyelectrolyte membranes with phosphonic acid functionality were prepared by acid-catalyzed sol–gel method, as a suitable alternative to perfluorinated membranes for the polyelectrolyte fuel cells applications. Phosphonic acid functional groups showed high intrinsic proton conductivity due to high mobility of protonic charge carriers and degree of self-dissociation, in the polymer matrix. Cross-linking was carried out by gluteraldehyde to achieve micro-tailoring in hydrophobic domain for polyelectrolyte membranes impervious to methanol. These membranes were designed to possess all the required properties of proton conductive membrane, namely reasonably swelling, good mechanical, dimensional and oxidative strength, flexibility, low methanol permeability along with reasonable proton conductivity due to bridged aromatic sulfone between functionalized silica. Higher thermal activated conduction process for synthesized membranes in comparison to Nafion 117 (N117) was responsible for slightly higher energy of activation for proton transfer. Moreover, from the estimation of selectivity parameter, 60% APDSPS composition among the PVA-APDSPS composite membranes showed highly suitable polyelectrolyte membrane, which suitability increased with the temperature.

Synthesis and Optical Properties of Bifunctional Thiophene Molecules Coordinated to Ruthenium

A series of unsymmetrical bi- and tetrathiophenes have been synthesized with bipyridine and phosphonic acid functional groups. To do this, phosphonic esters were bonded to thiophenes and the thiophenes coupled to bipyridine. After synthesis of the thienylbipyridines, bis(bipyridine) ruthenium was coordinated to them through the bipyridines. The thienylbipyridines absorb visible light and fluoresce; however, on attachment to ruthenium, both their fluorescence and that of ruthenium are quenched. An additional effect of coordinating ruthenium to the thiophenes is a new absorption band around 470 nm. Variation in oligothiophene length and bipyridine substitution position allowed comparison of the effect of these variables on electronic properties. The longer oligothiophenes display lower-energy absorptions and emissions than that of the shorter thiophenes. In contrast, the position of the bipyridine attachment does not have a large effect on the absorbance or emission wavelength, or on the fluorescence quantum yield.

Intermediate temperature proton conductors for PEM fuel cells based on phosphonic acid as protogenic group: A progress report

The melting behaviour and transport properties of straight chain alkanes mono- and difunctionalized with phosphonic acid groups have been investigated as a function of their length. The increase of melting temperature and decrease of proton conductivity with increasing chain length is suggested to be the consequence of an increasing ordering of the alkane segments which constrains the free aggregation of the phosphonic acid groups. However, the proton mobility is reduced to a greater extent than the proton diffusion coefficient indicating an increasing cooperativity of proton transport with increasing length of the alkane segment. The results clearly indicate that the "spacer concept", which had been proven successful in the optimization of the proton conductivity of heterocycle based systems, fails in the case of phosphonic acid functionalized polymers. Instead, a very high concentration of phosphonic acid functional groups forming "bulky" hydrogen bonded aggregates is suggested to be essential for obtaining very high proton conductivity. Aggregation is also suggested to reduce condensation reactions generally observed in phosphonic acid containing systems. On the basis of this understanding, the proton conductivities of poly(vinyl phosphonic acid) and poly(meta-phenylene phosphonic acid) are discussed. Though both polymers exhibit a substantial concentration of phosphonic acid groups, aggregation seems to be constrained to such an extent that intrinsic proton conductivity is limited to values below sigma = 10(-3) S cm(-1) at T = 150 degrees C. The results suggest that different immobilization concepts have to be developed in order to minimize the conductivity reduction compared to the very high intrinsic proton conductivity of neat phosphonic acid under quasi dry conditions. In the presence of high water activities, however, (as usually present in PEM fuel cells) the very high ion exchange capacities (IEC) possible for phosphonic acid functionalized ionomers (IEC >10 meq g(-1)) may allow for high proton conductivities in the intermediate temperature range (T approximately 120 -160 degrees C).

About the choice of the protogenic group in polymer electrolyte membranes: Ab initio modelling of sulfonic acid, phosphonic acid, and imidazole functionalized alkanes

The possible use of sulfonic acid, phosphonic acid, or imidazole as the protogenic group in polymer electrolyte membranes for fuel cells operating at intermediate temperature (T>100 degrees C) and very low humidity conditions is examined by comparing specific molecular properties obtained with first principles based electronic structure calculations. Potential energy profiles determined at the B3LYP/6-311G** level for rotation of imidazole, phosphonic acid and sulfonic acid functional groups on saturated heptyl chains revealed that the torsional barriers are 3.9, 10.0, and 15.9 kJ mol-1, respectively; indicating that the imidazole is clearly the most labile when tethered to an alkyl chain. Minimum energy conformations (B3LYP/6-311G**) of methyl dimers of each of the acids indicated that the binding of the pairs of the acids is greatest in the phosphonic acids and lowest for the imidazoles. Comparison of the ZPE corrected total energies of the methyl acid dimers with corresponding pairs consisting of the conjugate acid and conjugate base revealed that the energy penalty in transferring the proton (from acid to acid) was greatest for imidazole (120.1 kJ mol-1) and least for the phosphonic acid (37.2 kJ mol-1). This result is in agreement with experimentally measured proton conductivities of acid-functionalized heptyl compounds under dry conditions and further underpins the observation that phosphonic acid possesses the best amphoteric character critical in achieving proton conductivity when no solvent (i.e. water) is present. Finally, BSSE corrected binding energies were computed for the methyl acids with a single water molecule and indicated that while the magnitude of the interaction of the sulfonic and phosphonic acids with water are similar (47.3 and 44.4 kJ mol-1, respectively), the binding is much weaker to the imidazole (28.8 kJ mol-1). This result suggests that the oxo-acids will probably retain water better under very low humidity conditions and that the dynamics of the hydrogen bonding of the first hydration water molecules will be more constrained with -SO3H and -PO3H2 than imidazole.

Self-Assembly and Oligomerization of Alkyne-Terminated Molecules on Metal and Oxide Surfaces

We report the self-assembly and subsequent oligomerization of organic molecules based on terthiophenes bearing a terminal alkyne moiety. Molecules with thioacetate and phosphonic acid functional groups were synthesized, enabling molecular self-assembly on metal (Au and Pd) and metal oxide [Al(2)O(3), HfO(2), and indium tin oxide (ITO)] surfaces, respectively. The molecules were assembled from solution and then oligomerized using either 2,5-norbornadiene-rhodium(I) chloride dimer or UV light. UV-vis and infrared absorption spectroscopies and electrochemical techniques show that the molecules assemble to form dense monolayers on the substrate surfaces and oligomerize under the action of a catalyst or UV light.