Aryl ether-free polymer electrolytes for electrochemical and energy devices.

Anion exchange polymers (AEPs) play a crucial role in green hydrogen production through anion exchange membrane water electrolysis. The chemical stability of AEPs is paramount for stable system operation in electrolysers and other electrochemical devices. Given the instability of aryl ether-containing AEPs under high pH conditions, recent research has focused on quaternized aryl ether-free variants. The primary goal of this review is to provide a greater depth of knowledge on the synthesis of aryl ether-free AEPs targeted for electrochemical devices. Synthetic pathways that yield polyaromatic AEPs include acid-catalysed polyhydroxyalkylation, metal-promoted coupling reactions, ionene synthesis via nucleophilic substitution, alkylation of polybenzimidazole, and Diels-Alder polymerization. Polyolefinic AEPs are prepared through addition polymerization, ring-opening metathesis, radiation grafting reactions, and anionic polymerization. Discussions cover structure-property-performance relationships of AEPs in fuel cells, redox flow batteries, and water and CO2 electrolysers, along with the current status of scale-up synthesis and commercialization.

Migration and Precipitation of Platinum in Anion-Exchange Membrane Fuel Cells.

Despite the recent progress in increasing the power generation of Anion-exchange membrane fuel cells (AEMFCs), their durability is still far lower than that of Proton exchange membrane fuel cells (PEMFCs). Using the complementary techniques of X-ray micro-computed tomography (CT), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy, we have identified Pt ion migration as an important factor to explain the decay in performance of AEMFCs. In alkaline media Pt+2 ions are easily formed which then either undergo dissolution into the carbon support or migrate to the membrane. In contrast to PEMFCs, where hydrogen cross over reduces the ions forming a vertical "Pt line" within the membrane, the ions in the AEM are trapped by charged groups within the membrane, leading to disintegration of the membrane and failure. Diffusion of the metal components is still observed when the Pt/C of the cathode is substituted with a FeCo-N-C catalyst, but in this case the Fe and Co ions are not trapped within the membrane, but rather migrate into the anode, thereby increasing the stability of the membrane.

Electrode Separators for the Next-Generation Alkaline Water Electrolyzers.

Multi-gigawatt-scale hydrogen production by water electrolysis is central in the green transition when it comes to storage of energy and forming the basis for sustainable fuels and materials. Alkaline water electrolysis plays a key role in this context, as the scale of implementation is not limited by the availability of scarce and expensive raw materials. Even though it is a mature technology, the new technological context of the renewable energy system demands more from the systems in terms of higher energy efficiency, enhanced rate capability, as well as dynamic, part-load, and differential pressure operation capability. New electrode separators that can support high currents at small ohmic losses, while effectively suppressing gas crossover, are essential to achieving this. This Focus Review compares the three main development paths that are currently being pursued in the field with the aim to identify the advantages and drawbacks of the different approaches in order to illuminate rational ways forward.

Three-Dimensional Hollow Reduced Graphene Oxide Tube Assembly for Highly Thermally Conductive Phase Change Composites and Efficient Solar-Thermal Energy Conversion.

Due to their extraordinary mechanical strength and electrical and thermal conductivities, graphene fibers and their derivatives have been widely utilized in various functional applications. In this work, we report the synthesis of a three-dimensional (3D) hollow reduced graphene oxide tube assembly (HrGOTA) using the same wet spinning method as graphene fibers. The HrGOTA has high thermal conductivity and displays the unique capability of encapsulating phase change materials for effective solar-thermal energy conversion. The HrGOTA comprises layers of moisture-fused hollow reduced graphene oxide tubes (HrGOTs), whose individual thermal conductivity is up to 578 W m-1 K-1. By impregnating 1-octadecanol into HrGOTs, a 1-octadecanol-filled HrGOT phase change composite (PCC) with a latent heat of 262.5 J g-1 is obtained. This high latent heat results from the interfacial interaction between 1-octadecanol and the reduced graphene oxide tube, as evidenced by the shifts in XRD patterns of 1-octadecanol-filled and 1-octadecanol/multiwalled carbon nanotube-filled HrGOTA samples. In addition, 1 wt % multiwalled carbon nanotubes are added to the PCC to enhance visible light absorption. Because of their high thermal conductivity and visible light absorption rates, these new PCCs display high solar-thermal energy conversion and storage efficiencies of up to 81.7%, commensurate with state-of-the-art carbon-based PCCs but with significantly lower carbon weight percentages.

Properties of Anion Exchange Membranes with a Focus on Water Electrolysis.

Recently, alkaline membrane water electrolysis, in which membranes are in direct contact with water or alkaline solutions, has gained attention. This necessitates new approaches to membrane characterization. We show how the mechanical properties of FAA3, PiperION, Nafion 212 and reinforced FAA3-PK-75 and PiperION PI-15 change when stress−strain curves are measured in temperature-controlled water. Since membranes show dimensional changes when the temperature changes and, therefore, may experience stresses in the application, we investigated seven different membrane types to determine if they follow the expected spring-like behavior or show hysteresis. By using a very simple setup which can be implemented in most laboratories, we measured the "true hydroxide conductivity" of membranes in temperature-controlled water and found that PI-15 and mTPN had higher conductivity at 60 °C than Nafion 212. The same setup was used to monitor the alkaline stability of membranes, and it was found that stability decreased in the order mTPN > PiperION > FAA3. XPS analysis showed that FAA3 was degraded by the attack of hydroxide ions on the benzylic position. Water permeability was analyzed, and mTPN had approximately two times higher permeability than PiperION and 50% higher permeability than FAA3.

Rapid Synthesis of Silk-Like Polymers Facilitated by Microwave Irradiation and Click Chemistry.

Silk is a natural fiber that surpasses most man-made polymers in its combination of strength and toughness. Silk fibroin, the primary protein component of silk, can be synthetically mimicked by a linear copolymer with alternating rigid and soft segments. Strategies for chemical synthesis of such silk-like polymers have persistently resulted in poor sequence control, long reaction times, and low molecular weights. Here, we present a two-stage approach for rapidly synthesizing silk-like polymers with precisely defined rigid blocks. This approach utilizes solid-phase peptide synthesis to create uniform oligoalanine "prepolymers", followed by microwave-assisted step-growth polymerization with bifunctional poly(ethylene glycol). Multiple coupling chemistries and reaction conditions were explored, with microwave-assisted click chemistry yielding polymers with Mw ∼ 14 kg/mol in less than 20 min. These polymers formed antiparallel ß-sheets and nanofibers, which is consistent with the structure of natural silk fibroin. Thus, our strategy demonstrates a promising modular approach for synthesizing silk-like polymers.

One-Pot Synthesis of Proton Exchange Membranes from Anion Exchange Membrane Precursors.

Proton exchange membranes (PEMs) play a critical role in many electrochemical devices that could solve the shortcomings of current energy storage and conversion systems. Hydrocarbon-based PEMs are an attractive alternative for replacing the state-of-the-art perfluorosulfonic acid PEMs; however, synthetic routes are generally limited to sulfonation of aromatic units (pre- or postpolymerization functionalization). Here we disclose a facile and scalable one-pot synthetic method of converting an alkyl halide functionality to a sulfonate in polymer systems. With this method, sulfonated hydrocarbon PEMs can be conveniently prepared from a precursor polymer of anion exchange membranes which have recently experienced significant advances. Polyphenylene type PEMs (BPSA and mTPSA in this report) were generated in one-pot SN2 reaction of bromoalkyl side chains of polymers followed by oxidation. These PEMs showed excellent proton conductivity with BPSA showing 250 mS/cm in water at 80 °C, nearly 1.5 times higher than that of Nafion 212. Furthermore, the separation of the sulfonic acid group from the rigid backbone with a flexible alkyl chain mitigates excessive water uptake and in-plane swelling ratio of the polymer, despite having a high ion exchange capacity of 2.6 mequiv/g. Oxidative stability was also shown to be superior for hydrocarbon-based PEMs with negligible changes in mass, NMR, and proton conductivity.

Molecular Engineering of Hydroxide Conducting Polymers for Anion Exchange Membranes in Electrochemical Energy Conversion Technology.

Anion exchange membranes (AEMs) based on hydroxide-conducting polymers (HCPs) are a key component for anion-based electrochemical energy technology such as fuel cells, electrolyzers, and advanced batteries. Although these alkaline electrochemical applications offer a promising alternative to acidic proton exchange membrane electrochemical devices, access to alkaline-stable and high-performing polymer electrolyte materials has remained elusive until now. Despite vigorous research of AEM polymer design, literature examples of high-performance polymers with good alkaline stability at an elevated temperature are uncommon. Traditional aromatic polymers used in AEM applications contain a heteroatomic backbone linkage, such as an aryl ether bond, which is prone to degradation via nucleophilic attack by hydroxide ion. In this Account, we highlight some of the progress our group has made in the development of advanced HCPs for applications in AEMs and electrode ionomers. We propose that a synthetic polymer design with an all C-C bond backbone and a flexible chain-tethered quaternary ammonium group provides an effective solution to the problem of alkaline stability. Because of the critical demand for such a polymer system, we have established new synthetic strategies for polymer functionalization and polycondensation using an acid catalyst. The first approach is to graft a cationic tethered alkyl group to pre-existing, commercially available styrene-based block copolymers. The second approach is to synthesize high-molecular-weight aromatic backbone polymers using acid-catalyzed polycondensation of arene monomers and a functionalized trifluoromethyl ketone substrate. Both strategies involve a simple two-step reaction process and avoid the use of expensive metal-based catalysts and toxic chemicals, thereby making the synthetic processes easily scalable to large industrial quantities. Both polymer systems were found to have excellent alkaline stability, confirmed by the preservation of ion exchange capacity and ion conductivity of the membrane after an alkaline test under conditions of 1 M NaOH at 80-95 °C. In addition, the advantage of good solvent processability and convenient scalability of the reaction process generates considerable interest in these polymers as commercial standard AEM candidates. AEM fuel cell and electrolyzer tests of some of the developed polymer membranes showed excellent performance, suggesting that this new class of HCPs opens a new avenue to electrochemical devices with real-world applications.

Spectroscopic Characterization of Sulfonate Charge Density in Ion-Containing Polymers.

The charge density and hydrogen bonding with water of five different polymer membranes functionalized with various sulfonate side-chain chemistries were investigated using Fourier transform infrared (FTIR) techniques and density functional theory (DFT) calculations. The peak position of the OD stretch of dilute HOD absorbed into the sulfonated poly(sulfone) membranes was studied using FTIR to compare the charge density of the sulfonate headgroup across the different samples, which can ultimately be related to the acidity of the proton-form sulfonate moieties. The OD peak was deconvoluted to determine the percentage of headgroup-associated, intermediate, and bulk water. DFT modeling was used to calculate the charge density of each headgroup and visualize how the chemistry of the headgroup influenced the conformation of the side-chain tether. FTIR-determined OD peak positions and charge density calculations demonstrated that a perflurosulfonate containing a thioether linkage produced the most acidic sulfonate headgroup. However, the amount of headgroup-associated water calculated for this side chain was low due to the unique cis conformation of the thioether side chain. The biperfluorosulfonate side chain had very low calculated headgroup-associated water due to its bulkiness and water molecules bridging the two sulfonates. These detailed insights on local hydration of sulfonate side chains will point towards new headgroup designs for advanced membranes.

Poly(terphenylene) Anion Exchange Membranes: The Effect of Backbone Structure on Morphology and Membrane Property.

A new design concept for ion-conducting polymers in anion exchange membranes (AEMs) fuel cells is proposed based on structural studies and conformational analysis of polymers and their effect on the properties of AEMs. Thermally, chemically, and mechanically stable terphenyl-based polymers with pendant quaternary ammonium alkyl groups were synthesized to investigate the effect of varying the arrangement of the polymer backbone and cation-tethered alkyl chains. The results demonstrate that the microstructure and morphology of these polymeric membranes significantly influence ion conductivity and fuel cell performance. The results of this study provide new insights that will guide the molecular design of polymer electrolyte materials to improve fuel cell performance.

Fluorene-Based Hydroxide Ion Conducting Polymers for Chemically Stable Anion Exchange Membrane Fuel Cells.

Three novel fluorene-based polymers with pendant alkyltrimethylammonium groups were synthesized and characterized. The polymers were soluble in dimethylformamide, and dimethyl sulfoxide at room temperature and methanol at 40 °C while remaining insoluble in water. The polymeric membranes were transparent and flexible and exhibited hydroxide ion conductivities above 100 mS/cm at 80 °C. The results of 1H NMR and titration measurements demonstrated an excellent chemical stability of the synthesized polyfluorene, even after treatment in 1 M NaOH solution at 80 °C for 30 days. The results of this study suggest a feasible approach to the synthesis and practical applications of a new class of alkaline anion exchange membranes.

Robust Hydroxide Ion Conducting Poly(biphenyl alkylene)s for Alkaline Fuel Cell Membranes.

High molecular weight, quaternary ammonium-tethered poly(biphenyl alkylene)s without alkaline labile C-O bonds were synthesized via acid-catalyzed polycondensation reactions for the first time. Ion-exchange capacity was conveniently controlled by adjusting the feed ratio of two ketone monomers in the polymerization. The resultant anion exchange membranes showed high hydroxide ion conductivity up to 120 mS/cm and excellent alkaline stability at 80 °C. This study provides a new synthetic strategy for the preparation of anion exchange membranes with robust fuel cell performance and excellent stability.

FTIR characterization of water-polymer interactions in superacid polymers.

The OD stretch of dilute HOD in H2O absorbed in a series of sulfonated syndiotactic poly(styrene) and sulfonated poly(sulfone) membranes was studied using FTIR spectroscopy to measure how the character of the sulfonate head group and the backbone polarity influenced the water-membrane interactions. Using a three-state model, the OD stretch yielded information about the populations of absorbed water participating in hydrogen bonds with polymer-tethered sulfonate groups, water in an intermediate state, or water hydrogen bonding with other water molecules. The perfluoroalkyl sulfonate moiety, which behaves as a superacid, consistently displayed the largest fraction of head-group-associated water due to its strong acidic character. Measurements of the OD stretch gave insight into the strength of the hydrogen bonds formed between water and the sulfonate groups. Water associated with the superacid displayed an OD stretch peak position that was blueshifted by 39 cm(-1) compared to the aryl-sulfonate-associated water with an OD stretching frequency that was centered at 2547 cm(-1). The polarity of the polymer backbone also affected the OD stretch peak position. As hydration increased, the OD peak stretching frequency in poly(styrene)-based membranes displayed a red shift from 2566 to 2553 cm(-1), whereas there was no OD peak maxima shift in poly(sulfone)-based membranes due to the greater amount of intermediate water in the more polar poly(sulfone) backbone system.

Highly efficient incorporation of functional groups into aromatic main-chain polymer using iridium-catalyzed C-H activation and suzuki-miyaura reaction.

We report a mild, iridium-catalyzed borylation of aromatic polysulfone with bis(pinacolato)diboron [B(2)(pin)(2)] to form the corresponding borylated polysulfones up to high concentrations with nearly constant efficiency. The Suzuki-Miyaura cross-coupling reactions of the borylated polysulfones with functionalized aryl bromides allows installation of various functional groups such as ketone, amine, hydroxyl, and aldehyde to the polysulfone main chain in excellent conversion.

Nanoscale building blocks for the development of novel proton exchange membrane fuel cells.

We propose a new type of sulfonated aromatic polyarylenes as candidate building blocks for proton exchange membranes. Density functional theory calculations and ab initio molecular dynamics simulations suggest that desulfonation is limited at high temperatures, owing to the strong aryl-SO3H bond induced by the electron-deficient aromatic ring, and that the proposed polymers exhibit good thermomechanical stability due to the robust aromatic main-chain repeating unit. Simulations also emphasize the importance of the Grotthuss-type mechanism, with interconversion between Eigen (H9O4+) and Zundel cations (H5O2+) as limiting structures, for the hydrated proton transport in the vicinity of the sulfonic acid groups.

A fluorine containing bipyridine cisplatin analog is more effective than cisplatin at inducing apoptosis in cancer cell lines.

Novel cisplatin analogs dichloro[4,4'-bis(4,4,4-trifluorobutyl)-2,2'-bipyridine]platinum (1) and fac-tricarbonylchloro[4,4'-bis(4,4,4-trifluorobutyl)-2,2'-bipyridine]rhenium (3) were synthesized and evaluated for their cytotoxicity. While 3 was not cytotoxic, 1 was 14 to 125 times more lethal than cisplatin in breast, prostate, and lung cancer cell lines. Compound 1 was able to induce apoptosis and the presence of the platinum atom was essential to its function as a cytotoxin.

The question of C- vs. O-silylation of ketenes: electrophilic triethylsilylation of diphenylketene.

Electrophilic triethylsilylation of diphenylketene leads to exclusive C-silylation giving the diphenyl(triethylsilyl)acetyl cation in the solution phase even though density functional theory calculations at the B3LYP/6-311+G* level indicate that the O-silylation of diphenylketene is preferred over C-silylation by 5.4 kcal/mol in the gas phase. On the other hand, in the case of the parent ketene, similar density functional theory calculations show that C-silylation is preferred over O-silylation by 8.2 kcal/mol.

Catalytic hydroxylation of polypropylenes.

The regioselective functionalization of both model and commercial polypropylenes of varying tacticity has been conducted by a rhodium-catalyzed functionalization of the methyl C-H bonds of the polymer with diboron reagents. Rhodium-catalyzed borylation of the polypropylenes, followed by oxidation of the boron-containing material, produced polymers containing 0.2-1.5% hydroxymethyl side chains. Both the number-average molecular weights and molecular weight distributions of the polypropylenes were essentially unchanged after the catalytic and oxidative functionalization process. The efficiency of the borylation process was affected by the molecular weight of the polymer, the steric hindrance around the methyl groups, and the ratio of the diboron reagent to the monomer repeat unit. The hydroxylated derivative of the commercial isotactic polypropylene was used as macroinitiator for the aluminum-mediated ring-opening polymerization of epsilon-caprolactone to prepare polypropylene-graft-polycaprolactone. This graft copolymer was an effective compatibilizer for melt blends of polypropylene and polycaprolactone.

Regiospecific functionalization of methyl C-H bonds of alkyl groups in reagents with heteroatom functionality.

We report the regiospecific, rhodium-catalyzed borylation of saturated terminal C-H bonds in molecules with existing functionality. Moderate to good yields were obtained with the organic substrate in excess and as limiting reagent. The borylations of trialkylamines, protected alcohols, protected ketones, and fluoroalkanes occurred regiospecifically at the methyl group that is least sterically hindered. Reactions were also conducted that probed electronic effects on the alkyl borylation. These reactions showed that the borylation occurred preferentially at the methyl group that is most electron-deficient. Methods to conduct tandem borylation of C-H bonds and conversion of the resulting boronate esters to alcohols, alkylarenes, and alkyltrifluoroborates were also developed.