Mixed Zirconium Phosphate Bis-Phosphonomethyl Glycine from Nanocrystalline α-Zirconium Phosphate: A Tailored Suite for Gold Nanoparticles.

A novel synthetic approach was investigated for the preparation of nanoplatelets of mixed zirconium phosphate bis-phosphonomethyl glycine, ZPGly, by the reaction of a gel of nanocrystalline α-type zirconium phosphate with N,N-bis-phosphonomethyl glycine, H3Gly. The syntheses were carried out in the absence of hydrofluoric acid by changing both the reagent relative amounts and temperature. An H3Gly/Zr molar ratio >2 did not significantly improve the degree of crystallinity of the materials, while an increase of temperature from 80 °C to 120 °C improved the crystallinity; the best result was obtained with H3Gly/Zr molar ratio = 2 and with a temperature reaction of 120 °C. The sample consisted of nanoplatelets with the size in the range 20-40 nm, and it was successfully exfoliated by treatment with a solution of methylamine. By treatment of the ZPGly colloidal dispersions with HAuCl4, a color change from white to red-violet was observed, indicating the formation of gold nanoparticles. The size and morphology of the gold particles were affected by the degree of crystallinity and, in turn, by the composition of the ZPGly support. As a matter of fact, large micrometric Au particles with a cubo-octahedral morphology were obtained by using the less crystalline ZPGly_R2-80 sample, while interconnected Au particles, with a size of about 16 nm, were obtained by using ZPGly_R2-120. The samples exhibited an absorption maximum in the visible region due to the surface plasmon resonance of gold nanoparticles.

Treatment of Wastewaters with Zirconium Phosphate Based Materials: A Review on Efficient Systems for the Removal of Heavy Metal and Dye Water Pollutants.

Layered zirconium phosphate (ZrP) is a versatile material with phosphate (POH ) groups able to exchange inorganic and organic cations or to intercalate basic molecules. The present review deals with the use of this material as a sorbent for heavy metal cations or dye molecules in wastewater treatments. The possibility to combine ZrP with polymers or other inorganic materials, in order to have suitable systems for real and large scale applications, was investigated, as well as the combination with photocatalytic materials to obtain hetrogeneous photocatalysts for the capture and photodegradation of organic dye molecules.

Small is beautiful: the unusual transformation of nanocrystalline layered α-zirconium phosphate into a new 3D structure.

Nanosized α-zirconium phosphate, α-ZrP, undergoes a phase transition at 120 °C, which is not observed with microcrystalline α-ZrP in the same conditions, and which leads to a new 3D phase. The new compound, with formula Zr(HPO4)2 (τ'-ZrP), consists of cubelike nanoparticles and has a tetragonal unit cell (space group P43212, a = 7.955 Å, c = 10.744 Å). The structure of τ'-ZrP is in close relationship with that of the already known τ-ZrP. Both structures are made of packed chains of eight-membered rings, composed of Zr atoms connected to bridging HPO4 groups. The main difference between the two structures concerns the different orientation of the uncoordinated P-OH groups, pointing into the channels. The in situ XRPD analysis on nanosized α-ZrP, performed at 120 °C as a function of time, provided information about the kinetics of the formation of τ'-ZrP, showing that the α-ZrP phase is directly transformed into τ'-ZrP. Moreover, τ'-ZrP is converted into α-ZrP at room temperature in the presence of water vapor. It was proved that the free phosphoric acid, which is originally present in small amounts in nanosized α-ZrP and τ'-ZrP, is necessary for the interconversion between the two phases. As a matter of fact, the removal of phosphoric acid, by washing α-ZrP and τ'-ZrP with anhydrous ethanol, inhibits the above conversion.

Layered metal(IV) phosphonates with rigid pendant groups: new synthetic approaches to nanosized zirconium phosphate phenylphosphonates.

Single phase mixed zirconium phosphate phenylphosphonates, ZrP(PP)x, were prepared by two different synthetic approaches: reaction of gels of nanosized α-zirconium phosphate in propanol with solutions of phenylphosphonic acid (H2PP), leading to the topotactic exchange of monohydrogen phosphate groups with phenylphosphonate groups, and precipitation from propanol solutions of H2PP, phosphoric acid, and zirconyl propionate. In both cases, propanol intercalated compounds were obtained. The x values of the ZrP(PP)x materials prepared by topotactic anion exchange ranged from 0.37 to 0.56 for (H2PP/Zr) molar ratios in the range 0.52-4.16 and [H2PP] = 0.1 M, while a maximum x value of 0.73 was only reached at 60 °C, with (H2PP/Zr) = 4.16 and [H2PP] = 0.31 M. Direct precipitation of ZrP(PP)x provided samples with 0.13 ≤ x ≤ 1.54, for H2PP molar fractions in the range 0.05-0.5 and (P/Zr) molar ratio = 6. At 90% relative humidity, the (H2O/Zr) molar ratio for the precipitated ZrP(PP)x powder samples increased in the range 1.3-3.0 with increasing x and resulted in being higher than that of nanosized ZrP (0.8). The analysis of the X-ray diffraction patterns of the gel and powder samples, together with the hydration data of the powder samples, suggested a structural model in which the random distribution of the phosphate and phenylphosphonate groups creates cavities which can accommodate propanol molecules in the gel samples and water molecules in the hydrated powder samples.

Looking for new hybrid polymer fillers: synthesis of nanosized α-type Zr(IV) organophosphonates through an unconventional topotactic anion exchange reaction.

Gels of α-type zirconium(IV) phosphate alkylphosphonates, ZP(Cn)x, were prepared by reacting, at room temperature, propanol intercalated nanosized α-zirconium phosphate (α-ZrP) with propanol solutions of alkylphosphonic acids (H2Cn, n = number of carbon atoms in the alkyl chain = 4, 5, 6), with (H2Cn/Zr) molar ratios in the range 0.4-4.0. (31)P MAS NMR showed the presence of resonances due to the phosphate and phosphonate groups bonded to the Zr atoms mainly by three oxygen atoms, as in the α-type layer. The composition of the ZP(Cn)x materials, obtained by thermogravimetric analysis, ranges from x ≈ 0.2 to x ≈ 1.1. On the basis of the NMR data and of the analysis of the X-ray patterns of gels and powders, it is inferred that the ZP(Cn)x compounds have an α-type layered structure and that the reaction between α-ZrP and H2Cn is a topotactic anion exchange process. The evolution of the X-ray patterns during propanol deintercalation is consistent with a random distribution of the alkylphosphonate groups on the α-type layers which gives rise to porous pathways in the interlayer region. To test the possibility of using ZP(Cn)x as mechanical reinforcement of a polymer matrix, a starch membrane filled with 5 wt % ZP(C6)0.54 was prepared and characterized by stress-strain mechanical tests. Besides an excellent flexibility, this membrane exhibited a proportional increase of the Young's modulus by 230% in comparison with neat starch.

Overcoming Antibiotic Resistance: Playing the 'Silver Nanobullet' Card.

Enhancing the antibacterial activity of old antibiotics by a multitarget approach, such as combining antibiotics with metal nanoparticles, is a valuable strategy to overcome antibacterial resistance. In this work, the synergistic antimicrobial effect of silver nanoparticles and antibiotics, immobilized on a solid support, was investigated. Nanometric layered double hydroxides (LDH) based on Zn(II) and Al(III) were prepared by the double microemulsion technique. The dual function of LDH as an anionic exchanger and support for metal nanoparticles was exploited to immobilize both silver and antibiotics. Cefazolin (CFZ), a ß-lactam, and nalidixic acid (NAL), a quinolone, were selected and intercalated into LDH obtaining ZnAl-CFZ and ZnAl-NAL samples. These samples were used for the growth of silver nanoparticles with dimension ranging from 2.5 to 8 nm. Silver and antibiotics release profiles, from LDH loaded with antibiotics and Ag/antibiotics, were evaluated in two different media: water and phosphate buffer. Interestingly, the release profiles are affected by both the acceptor media and the presence of silver. The synergistic antibacterial activity of LDH containing both silver and antibiotics were investigated on gram-positives (Staphylococcus aureus and Streptococcus pneumoniae) and gram-negatives (Pseudomonas aeruginosa) and compared with the plain antimicrobials and LDH containing only antibiotics or silver.

Advances in the chemistry of nanosized zirconium phosphates: a new mild and quick route to the synthesis of nanocrystals.

Simple addition of zirconyl propionate to phosphoric acid in alcoholic media surprisingly led to the formation, in few minutes, of transparent gels containing solvent intercalated zirconium phosphate (ZrP) nanoparticles with hexagonal shape and a planar size of about 40 nm. With the help of elemental analysis, inductively coupled plasma-optical emission spectrometry (ICP-OES), and (31)P magic angle spinning (MAS) NMR, the nanoparticle composition was formulated as Zr(R)(w)(HPO(4))(x)(H(2)PO(4))(y), in which R can be an hydroxyl or a propionate group. The stoichiometric coefficients for propanol intercalated ZrP are x = 1.43, y = 0.83, and w = 0.32. Solvent elimination at 60 °C gave rise to an increase in the x value and a decrease in the y and w values. X-ray powder diffraction analysis and transmission electron microscopy (TEM) observations showed a concomitant increase in the particle size: planar size and thickness ranged from 90 to 200 nm and from 20 to 85 nm, respectively, depending on the nature of the solvent. A possible mechanism explaining the change in the x, y, and w values, the growth of nanoparticles, and the role of the solvent is proposed. Finally, the possibility of using these gels to disperse the ZrP nanoparticles within the polymer matrix of Nafion117 is shown.

Biofunctionalization of Poly(lactide-co-glycolic acid) Using Potent NorA Efflux Pump Inhibitors Immobilized on Nanometric Alpha-Zirconium Phosphate to Reduce Biofilm Formation.

Polymeric composites, where bioactive species are immobilized on inorganic nanostructured matrix, have received considerable attention as surfaces able to reduce bacterial adherence, colonization, and biofilm formation in implanted medical devices. In this work, potent in-house S. aureus NorA efflux pump inhibitors (EPIs), belonging to the 2-phenylquinoline class, were immobilized on nanometric alpha-zirconium phosphate (ZrP) taking into advantage of acid-base or intercalation reactions. The ZrP/EPI were used as filler of poly(lactide-co-glycolic acid) (PLGA) to obtain film composites with a homogeneous distribution of the ZrP/EPI fillers. As reference, PLGA films loaded with ZrP intercalated with thioridazine (TZ), that is recognized as both a NorA and biofilm inhibitor, and with the antibiotic ciprofloxacin (CPX) were prepared. Composite films were characterized by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The ability of the composite films, containing ZrP/EPI, to inhibit biofilm formation was tested on Staphylococcus aureus ATCC 29213 and Staphylococcus epidermidis ATCC 12228, and it was compared with that of the composite loaded with ZrP/TZ. Finally, the antibacterial activity of CPX intercalated in ZrP was evaluated when used in combination with ZrP/EPI in the PLGA films.

Polydopamine Coated CeO2 as Radical Scavenger Filler for Aquivion Membranes with High Proton Conductivity.

CeO2 nanoparticles were coated with polydopamine (PDA) by dopamine polymerization in water dispersions of CeO2 and characterized by Infrared and Near Edge X-ray Absorption Fine Structure spectroscopy, Transmission Electron Microscopy, Thermogravimetric analysis and X-ray diffraction. The resulting materials (PDAx@CeO2, with x = PDA wt% = 10, 25, 50) were employed as fillers of composite proton exchange membranes with Aquivion 830 as ionomer, to reduce the ionomer chemical degradation due to hydroxyl and hydroperoxyl radicals. Membranes, loaded with 3 and 5 wt% PDAx@CeO2, were prepared by solution casting and characterized by conductivity measurements at 80 and 110 °C, with relative humidity ranging from 50 to 90%, by accelerated ex situ degradation tests with the Fenton reagent, as well as by in situ open circuit voltage stress tests. In comparison with bare CeO2, the PDA coated filler mitigates the conductivity drop occurring at increasing CeO2 loading especially at 110 °C and 50% relative humidity but does not alter the radical scavenger efficiency of bare CeO2 for loadings up to 4 wt%. Fluoride emission rate data arising from the composite membrane degradation are in agreement with the corresponding changes in membrane mass and conductivity.

Organically modified zirconium phosphate by reaction with 1,2-epoxydodecane as host material for polymer intercalation: synthesis and physicochemical characterization.

Organically modified alpha-layered zirconium phosphate samples (ZrP(C(12))(x)) containing dodecyl groups bonded to the alpha-layers through P-O-C bonds have been prepared by reaction of 1,2-epoxydodecane solutions in tetrahydrofuran (THF) with gels of partially exfoliated zirconium phosphate in THF. Two dimensional correlation solid state NMR experiments for (1)H-(13)C and (1)H-(31)P nuclei have been used to prove the formation of P-O-C bonds arising from nucleophilic attack of POH mainly to carbon 1 and, to a lesser extent, to carbon 2 of epoxydodecane. ZrP(C(12))(x) samples with x in the range from approximately 0.5 to approximately 2.0 are thermally stable up to at least 200 degrees C, and their interlayer distance increases continuously with x from approximately 20 to approximately 35 A. On the basis of structural considerations, it has been suggested that samples with low x values could intercalate aliphatic polymers. Accordingly, preliminary results have shown that molten polyethylene is intercalated in ZrP(C(12))(0.49) and ZrP(C(12))(0.73). These materials can therefore be regarded as filler candidates for polymer matrixes.

A new challenge for nanocrystalline α-zirconium phosphate: reaction with a diepoxyalkane.

New organic derivatives of α-zirconium phosphate (ZrP) were prepared by reaction of a gel of nanocrystalline ZrP with 1,2,7,8-diepoxyoctane (diepoxide), leading to the formation of P-O-C bonds. A series of compounds having composition Zr(O3POH)2-2x(O3POCH2CH(OH)(CH2)4CH(OH)CH2OPO3)x (hereafter indicated as ZrP(dep)x) were obtained by varying the diepoxide/Zr molar ratio in the range 0.25-1. The samples were characterized by elemental, thermal and X-ray powder diffraction analysis. The reaction turned out to be nearly quantitative, the x values of ZrP(dep)x being in the range 0.16 to 1.0. The interlayer distance slightly increased with increasing x, going from 12.7 to 13.2 Å. Interestingly, the materials easily intercalated alkanols at room temperature, both from liquid and vapor phases; it is noteworthy that ZrP(dep)0.30 was able to reversibly take up 42 wt% ethanol from the vapor phase, in agreement with the presence of available free space both in the interlayer and in the intercrystal region. Geometrical structural models in which the α-ZrP layers are connected by the dep chains were proposed to support the obtained results.

Preparation of nano-structured polymeric proton conducting membranes for use in fuel cells.

We briefly discuss the state of the art of polymer electrolyte membrane fuel cells and suggest that the main obstacles to the commercial development of these fuel cells are essentially the high costs and poor characteristics of present proton conducting membranes. A strategy for the preparation of improved nanocomposite membranes based on the introduction of proton conducting lamell? in the polymeric matrix of present ionomeric membranes is then discussed. Due to their high proton conductivity (in some cases even higher than 10(-1) S cm(-1)), tailor made lamellae obtained by exfoliation of superacid metal (IV) phosphonates are particularly suitable for the preparation of these hybrid membranes. The expected positive influence of the dispersed lamellae on important properties of proton conducting membranes, such as swelling, mechanical resistance, proton transport, and diffusion of methanol, are also discussed. The methods used to obtain good lamellar dispersions into ionomeric polymers and the preparation and main characteristics of some hybrid membranes are also briefly described. The presence of nanoparticles of metal phosphonates in the electrodic interfaces Nafion/Pt already considerably improves the electrochemical characteristics of fuel cells in the temperature range 80-130 degrees C. The increased working temperature of the fuel cell considerably reduces CO poisoning of the platinum electrodes and allows better control of the cooling system, thus overcoming important obstacles to the development of medium temperature PEM fuel cells.

Dynamic nuclear polarisation NMR of nanosized zirconium phosphate polymer fillers.

Surface functionalisation with organic modifiers of multi-layered zirconium phosphate (ZrP) nanoparticles used as polymer fillers can be directly probed by dynamic nuclear polarisation NMR, which provides unambiguous evidence of the presence of P-O-C chemical bonds at the surface of the ZrP layers, thereby confirming successful functionalisation.

Promising aquivion composite membranes based on fluoroalkyl zirconium phosphate for fuel cell applications.

Layered zirconium phosphate (ZP) that bears fluorinated alkyl chains bonded covalently to the layers (ZPR) was used as a nanofiller in membranes based on a short-side-chain perfluorosulfonic acid (PFSA) to mechanically reinforce the PFSA hydrophobic component. Compared to the pristine PFSA, membranes with a ZPR loading up to 30 wt% show enhanced mechanical properties, and the largest improvement of elastic modulus (E) and yield stress (σY ) are observed for the 10 wt% ZPR membrane: ΔE/E up to 90% and ΔσY /σY up 70% at 70°C and 80% relative humidity (RH). In the RH range 50-95%, the in-plane conductivity of the composite membranes reaches 0.43 S cm(-1) for 10 wt% ZPR at 110°C and is on average 30% higher than the conductivity of the pristine PFSA. The 10 wt % ZPR membrane is as hydrated as the neat PFSA membrane at 50% RH but becomes progressively less hydrated with increasing RH both at 80 and 110°C. The fuel cell performance of this membrane, at 80°C and 30% RH, is better than that of the unmodified PFSA.

Aminoalcohol functionalized zirconium phosphate as versatile filler for starch-based composite membranes.

Microcrystalline zirconium phosphate was exfoliated by treatment with aqueous solutions of α,ω-alkylaminoalcohols and employed for the fabrication of potato starch composite membranes. Glycerol-based and glycerol-free composite membranes, containing 5 wt% of filler, were prepared from gelatinized starch and characterized for their physico-chemical properties. Despite of a partial filler reaggregation, as revealed by XRD and SEM analysis, all the composites exhibited a significant increase in the Young's modulus with respect to the glycerol-starch membrane, up to 80% and 190% for the glycerol-based and the glycerol-free composites, respectively. For both kinds of membranes the filler delays to a large extent the starch decomposition above about 300°C. A significant reduction in the water uptake of the composites was also observed with respect to the neat glycerol-based membrane, up to about 70% for the glycerol-free composites.