Synthesis and properties of sulfonated poly[bis(benzimidazobenzisoquinolinones)] as hydrolytically and thermooxidatively stable proton conducting ionomers

Novel sulfonated poly [bis(benzimidazobenzisoquinolinones)] as hydrolytically and thermooxidatively stable electrolyte for high -temperature fuel cell applications are reported. A series of sulfonated polymers (SPBIBI-x, x refers to molar percentage of sulfonated dianhydride monomer) were synthesized from 6,6'-disulfonic-4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (SBTDA), 4,4-binaphthyl-1,1,8,8-tetracarboxylic dianhydride (BTDA), and 3,3'-diaminobenzidine. The chemical structures of those polymers as well as model compounds synthesized from SBTDA and o-phenylenediamine were confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR).

Synthesis and properties of novel polyimides from sulfonated binaphthalene dianhydride for proton exchange membranes

A sulfonated dianhydride monomer, 6,6-disulfonic-4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (SBTDA), was successfully synthesized by direct sulfonation of the parent dianhydride, 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), using fuming sulfuric acid as the sulfonating reagent. A series of sulfonated homopolyimides were prepared from SBTDA and various common nonsulfonated diamines. The resulting polymer electrolytes, which contain ion conductivity sites on the deactivated positions of the aryl backbone rings, displayed high proton conductivities of 0.25-0.31 S cm(-1) at 80 degrees C. The oxidative stability test indicated that the attachment of the -SO3H groups onto the dianhydride units did not deteriorate the oxidative stability of the SPI membranes.

Synthesis of sulfonated poly(arylene-co-naphthalimide)s as novel polymers for proton exchange membranes

A series of novel sulfonated poly(arylene-co-binaphthalimide)s (SPPIs) were successfully synthesized via Ni(0) catalytic coupling of sodium 3-(2,5-dichlorobenzoyl)benzenesulfonate and bis(chloronaphthalimide)s. Bis(chloronaphthalimide)s were conveniently prepared from 5-chloro-1,8-naphthalic anhydride and various diamines. Tough and transparent SPPI membranes were prepared and the electrolyte properties of the copolymers were intensively investigated as were the effects of different diamine structures on the copolymer characterisitics. The copolymer membrane Ia-80, with an ion exchange capacity (IEC) of 2.50 meq g(-1), displayed a higher proton conductivity, i.e. 0.135 S cm(-1) at 20 degrees C, as compared to Nafion 117 (0.09 S cm(-1), 20 degrees C).

Novel acid-base polyimides synthesized from binaphthalene dianhydrie and triphenylamine-containing diamine as proton exchange membranes

The synthesis and characterization of novel acid-base polyimide membranes for the use in polymer electrolyte membrane fuel cell is presented in this paper. The sulfonated polyimides (SPIs) bearing basic triphenylamine groups were easily synthesized using 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), sulfonated diamine of 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid (ODADS), and nonsulfonated diamines of 4,4'-diaminotriphenylamine (DATPA). The effects of the structure of the dianhydride and diamines on the properties of SPI membranes were evaluated through the study of membrane parameters including water sorption, proton conductivity, water stability, dimensional changes, and methanol permeability.

Carbon nanotubes decorated with Pt nanocubes by a noncovalent functionalization method and their role in oxygen reduction

Combined with polymer wrapping and layer-by-layer techniques, a noncovalent functionalization method is developed to disperse Pt nanocubes (NCs) onto carbon nanotubes (CNTs). By adjusting the relative ratio of Pt NCs to CNTs, nanotubes with different Pt NC loadings are produced. The composites exhibit excellent electrocatalytic activity towards oxygen reduction.

Preparation of Pd/C catalyst for formic acid oxidation using a novel colloid method

A novel colloid method using (WO3)(n)center dot xH(2)O as colloidal source was developed to prepare Pd/C catalyst for formic acid oxidation. Transmission electron microscopy image shows that the Pd/C nanoparticles have an average size of 3.3 nm and a narrow size distribution. Electrochemical measurements indicate that the Pd/C catalyst exhibits significantly high electrochemical active surface area and high catalytic activity with good stability for formic acid oxidation compared with that prepared by common method.

Highly active PtRu catalysts supported on carbon nanotubes prepared by modified impregnation method for methanol electro-oxidation

A simple and rapid synthesis method (denoted as modified impregnation method, MI) for PtRu/CNTs (MI) and PtRu/C (MI) was presented. PtRu/CNTs (MI) and PtRu/C (MI) catalysts were characterized by transmission electron microscopy (TEM) and X-ray diffractometry. It was shown that Pt-Ru particles with small average size (2.7 nm) were uniformly dispersed on carbon supports (carbon nanotubes and carbon black) and displayed the characteristic diffraction peaks of Pt face-centered cubic structure.

Novel Sulfonated Polyimide Ionomers by Incorporating Pyridine Functional Group in the Polymer Backbone

A series of sulfonated polyimides (SPIs) containing pyridine ring in the polymer backbone were synthesized by the polycondensation of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTDA), 5-(2,6-bis(4-arninophenyl)pyridin-4-yl)-2-methoxy benzene sulfonic acid (SDAM), and 4,4'-diaminodiphenyl ether (ODA). Flexible, transparent, and tough membranes were obtained. Property study revealed that all the membranes displayed high thermal stability with the desulfonation and decomposition temperature higher than 290 and 540 degrees C, respectively, as well as good mechanical property with Young's modulus larger than 1.0 GPa, maximum strength (MS) on a scale of 60-80 MPa, and elongation at break (EB) ranged from 41.79 to 75.17%.

Naphthalene-Based Poly(arylene ether ketone) Copolymers Containing Sulfobutyl Pendant Groups for Proton Exchange Membranes

A new monomer 1,5-bis(4-fluorobenzoyl)-2,6-dimethoxynaphthalene (DMNF) was prepared and further polymerized to form naphthalene-based poly(arylene ether ketone) copolymers containing methoxy groups (MNPAEKs). The side-chain-type sulfortated naphthalene-based poly(arylene ether ketone) copolymers (SNPAEKs) were obtained by demethylation and sulfobutylation. Flexible and tough membranes with reasonably high mechanical strength were prepared. The SNPAEKs membrane showed anisotropic membrane swelling with larger swelling in thickness than in plane. Transmission electron microscopy (TEM) analysis revealed clear nano-phase separated structure of SNPAEKs membranes, which composed of hydrophilic side chain and hydrophobic main-chain domains.

Novel Hybrid Electrocatalyst with Enhanced Performance in Alkaline Media: Hollow Au/Pd Core/Shell Nanostructures with a Raspberry Surface

In this paper, a hollow Au/Pd core/shell nanostructure with a raspberry surface was developed for methanol, ethanol, and formic acid oxidation in alkaline media. The results showed that it possessed better electrocatalyst performance than hollow Au nanospheres or Pd nanoparticles. The nanostructure was fabricated via a two-step method. Hollow Au nanospheres were first synthesized by a galvanic replacement reaction, and then they were coated with a layer of Pd grains. Several characterizations such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS) were used to investigate the prepared nanostructures.

Dispersions of carbon nanotubes in sulfonated poly[bis(benzimidazobenzisoquinolinones)] and their proton-conducting composite membranes

A sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI) possessing a conjugated pyridinone ring was shown to be effective for dispersing multiwalled carbon nanotubes (MWCNTs) in DMSO. The dispersions in which the SPBIBI to MWCNTs mass ratio was 4:1 demonstrated the highest MWCNTs concentrations, i.e., 1.5-2.0 mg mL(-1), and were found to be stable for more than six months at room temperature. Through casting of these dispersions, MWCNTs/SPBIBI composite membranes were successfully fabricated on substrates as proton exchange membranes for fuel cell applications and showed no signs of macroscopic aggregation. The properties of composite membranes were investigated, and it was found that the homogeneous dispersion of the MWCNTs in the SPBIBI matrix altered the morphology structures of the composite membranes, which lead to the formation of more regular and smaller cluster-like ion domains.

Novel hydrophilic-hydrophobic multiblock copolyimides as proton exchange membranes: Enhancing the proton conductivity

A series of novel multiblock copolymers based on sulfonated copolyimides were developed and evaluated for use as proton exchange membranes (PEMs). In these multiblock copolyimides, the hydrophilic blocks were composed of the sulfonated dianhydride and the sulfonated diamine, with sulfonic acid groups on every aromatic ring (i.e., fully sulfonated). This molecular design was implemented to effectively enhance the proton conductivity. The properties of the multiblock copolyimides with varying IEC values or block lengths were investigated to obtain a better understanding of the relationship between molecular structure and properties of proton exchange membranes. The water uptake and proton conductivity were found to be highly dependent upon their structure. The block copolymers displayed significantly higher proton conductivities, especially at low relative humidity than the random copolymers with a similar IEC.

Synthesis and properties of novel sulfonated poly(phenylquinoxaline)s as proton exchange membranes

Two series of sulfonated poly(phenylquinoxaline)s (SPPQ-x and SPPQ(O)-x, x refers to molar percentage of sulfonated tetraamine monomer) were first synthesized from a sulfonated tetraamine (4,4'-bis(3,4-diaminophenoxy)biphenyl-3.3'-disulfonic acid) and two aromatic bisbenzils (4-phenylglyoxalylbenzil and p,p'-oxydibenzil) in a mild condition. The structures of SPPQ-x and SPPQ(0)-x were characterized by IR and H-1 NMR spectra. The properties of these polymer films, such as water uptake, water swelling ratio, proton conductivity, thermal properties, methanol permeability, hydrolytic and oxidative stability were also investigated. The resulting polymers generally showed good solubility in DMAc and DMSO. Flexible and tough membranes with high mechanical strength were prepared. They show very high thermal, thermooxidative, hydrolytic stabilities and low methanol permeability. SPPQ-100 with the IEC value (2.41 mmol/g) displays the conductivity of 0.1 S/cm and a swelling ratio of 7.3% at 100 degrees C.

Novel proton exchange membranes based on water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)]

Novel water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBIs) were synthesized from 6,6'-disulfonic-4,4'-binaphthy]-1,1',8,8'-tetracarboxylic dianhydride (SBTDA) and various aromatic ether tetraamines. The resulting polymers with IEC in the range of 2.17-2.87 mequiv g(-1) have a combination of desired properties such as high solubility in common organic solvents, film-forming ability, and excellent thermal and mechanical properties. Flexible and tough membranes, obtained by casting from m-cresol solution, had tensile strength, elongation at break, and tensile modulus values in the range of 87.6-98.4 MPa, 35.8-52.8%, and 0.94-1.07 GPa. SPBIBI membranes with a high degree of sulfonation displayed high proton conductivity and a good resistance to water swelling as well. SPBIBI-b with IEC of 2.80 mequiv g(-1) displayed the conductivity of 1.74 x 10(-1) S cm(-1) at 100 degrees C, which was comparable to that of Nafion (R) 117 (1.78 x 10(-1) S cm(-1), at 100 degrees C).

High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH4)(2)PtCl6 and Ru(OH)(3)) on the carbon support before metal reduction: the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method. even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst.