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Comparing Ammonium and Tetraaminophosphonium Anion-Exchange Membranes Derived from Vinyl-Addition Polynorbornene Copolymers
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Phenyl‐Free Polynorbornenes for Potential Anion Exchange Ionomers for Fuel Cells and Electrolyzers
Abstract Ionomers in the catalyst layer play a critical role in the performance of fuel cells and electrolyzers. Phenyl adsorption on hydrogen oxidation catalysts and electrochemical oxidation of phenyl moieties on oxygen evolution catalysts are detrimental to the alkaline devices’ performance. Here the adsorption energy of phenyl‐containing ionomers is compared to provide the rationale for implementing phenyl‐free ionomers. Density functional theory calculations indicated that the norbornane fragment has minimal adsorption energy on Pt(111) due to the absence of aromatic π electrons. A soluble quaternized polynorbornene ionomer is prepared by vinyl addition polymerization, and it exhibits high performance in both fuel cells and electrolyzers, proving the advantage of the phenyl‐free structure. This study establishes the phenyl adsorption energy‐electrode performance relationship, highlighting the importance of material interactions between the catalysts and ionomers.
Optimization of anionic conductivity through the coexistence of ionomer cluster and backbone-backbone morphologies in anion exchange membranes
Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2-8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3-6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60 degrees C. Finally, conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90 degrees C.
Regeneration of anion-exchange resins for cyclic selenium removal from industrial wastewaters
Application of ion exchange for the removal of selenium (Se) oxyanions from industrial wastewaters is often limited by ineffective regeneration of the ion-exchange resins, particularly in complex systems containing competing ions, such as coal-ash leachate containing high-sulfate concentrations and heavy metal ions. Here, in this study, it was first demonstrated that while conventional regeneration with sodium chloride (NaCl) is effective for simulated wastewater, with ∼80% efficiency, NaCl fails to regenerate resin loaded with real industrial wastewater, achieving less than 20% efficiency. To overcome this challenge, a two-step regeneration process was investigated using a sodium carbonate (Na 2 CO 3 ) solution for elution, followed by a NaCl solution for restoration. Compared to the one-step NaCl regeneration, this integrated process restored more than 80% of the resin's capacity with real industrial wastewaters. Beyond demonstrating regeneration performance, this research emphasizes fundamental mechanistic interpretations of the observed regeneration behavior across different water matrices and experimental conditions. Particularly, accounting for pH-dependent carbonate speciation, it is proposed that the elution step exploits the resin's strong affinity for divalent carbonate ions to displace strongly bound contaminants, while the subsequent restoration step relies mainly on the mass action effects of chloride ions to regenerate the resin sites. The protocol was optimized to achieve rapid regeneration (<10 min) using moderate chemical concentrations (0.5 M) in treating real leachate. In batch cyclic experiments, Se regeneration reached nearly complete recovery after five consecutive sorption and desorption cycles, while in the fixed-bed system, the regeneration efficiency remained at approximately 80% after five cycles.
Anion exchange membranes: The effect of reinforcement in water and electrolyte
Alkaline anion-conducting polymer-based CO 2 electrolysis and water electrolysis are among two emerging renewable energy conversion technologies. Their system design and integration offer promise of lower capital cost due to utilization of low-cost catalysts, in contrast to platinum group metal catalysts required for cation-conducting polymer-based devices. However, a critical component, the polymer electrolyte membrane, remains an obstacle hampering system performance and durability. In this study, commercially-available Sustainion® membranes with and without PTFE-reinforcement were investigated to understand previously unreported origins of improved device performance when compared to alternative membrane chemistries. We report critical membrane properties, such as morphology, thermal stability, as well as temperature-, hydration-, and counter-ion dependent ion conductivity. Moveover, the changes in uptake and conductivity of membranes in supporting electrolytes of K 2 CO 3 and KOH investigated as a function of their concentration. Presence of reinforcement and supporting electrolyte type alter the membrane's transport functionality, which could help guide device design for improved performance. In conclusion, the obtained results not only show how Sustainion® properties change with operating environment for CO 2 and water electrolysis applications, but also provide understanding for internal and external factors controlling anion-exhcnage membrane functionality in electrochemical devices.
The anion exchange properties of AFm (hydrocalumite-group) minerals defined from solubility experiments and crystallographic information
Solubility experiments with binary series of OH-, Cl-, SO{sub 4}- and CO{sub 3}-AFm were re-examined with a non-ideal, multicomponent solid solution model. The electrical double layer on the mineral's outer surface, which neutralizes about 5% of the anionic charge, can be included. The choice of the end-members in the solid solution and the reaction formulation can help to eliminate the ‘non-ideality’ for OH-SO{sub 4} and Cl-OH exchange. CO{sub 3}-Cl-OH exchange is not ideal in the solubility experiments, nor can it be, because the mineral volume is not a linear combination of the end-members. The solubilities of the end-members are related to the anion charge and inversely to the anion-layer thickness. OH is part of the anion-charge, even when a pure, other anion form is the target of the synthesis. Pure OH-AFm is unstable and converts into hydrogarnet and portlandite, depending on the precipitation rate of hydrogarnet.
Anion exchange membranes for electrochemical oxidation-reduction energy storage system
Oxidation-reduction couples in concentrated solutions separated by appropriate ion selective membranes were considered as an attractive approach to bulk electrical energy storage. A key problem is the development of the membrane. Several promising types of anionic membranes are discussed which were developed and evaluated for redox energy storage systems. The copolymers of ethyleneglycoldimethacrylate with either 2-vinylpyridine or vinylbenzl chloride gave stable resistance values compared to the copolymer of vinylbenzlchloride and divinylbenzene which served as the baseline membrane. A polyvinylchloride film aminated with tetraethylenepentamine had a low resistance but a high ion transfer rate. A slurry coated vinylpyridine had the lowest ion transfer rate. All these membranes functioned well in laboratory cells at ambient temperatures with the acidic chloride oxidant/reductant system, Fe 3, Fe 2/Ti 3, Ti 4.
Comparing Intrinsic Catalytic Activity and Practical Performance of Ni- and Pt-Based Alkaline Anion Exchange Membrane Water Electrolyzer Cathodes
The stringent cost and performance requirements of renewable hydrogen production systems dictate that electrolyzers benefit from the use of nonprecious catalysts only if they deliver the same level of activity and durability as their precious metal counterparts. Here we report on recent work to understand interrelationships between the intrinsic activity of Ni- and Pt-based electrolyzer cathode catalysts and their performance in zero-gap alkaline water electrolyzer assemblies. Our results suggest that nanoparticulate Ni–Mo exhibits HER activity that is roughly 10-fold lower than Pt–Ru on the basis of turnover frequency under low (≤100 mV) polarization conditions. We further found that the HER activity of Ni–Mo/C cathodes is inhibited by aryl piperidinium anionexchange ionomers bearing bicarbonate counter-anions. After addressing this poisoning effect, we produced electrolyzer assemblies based on Ni–Mo/C cathodes that delivered indistinguishable current density vs cell potential relationships compared to otherwise identical assemblies with Pt–Ru cathodes. This result indicates that the contribution of the cathode to the total cell polarization is small, even for the less active Ni–Mo/C catalyst, and further implies that Pt-based cathodes can indeed be replaced by nonprecious alternatives with no loss in performance.
Reshaping the Cathodic Catalyst Layer for Anion Exchange Membrane Fuel Cells: From Heterogeneous Catalysis to Homogeneous Catalysis
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Exploring Phosphonium‐Based Anion Exchange Polymers for Moisture Swing Direct Air Capture of Carbon Dioxide
This study explores the performance and stability of ammonium and phosphonium-based polymeric ionic liquids (PILs) with methyl and butyl substituents in moisture-swing direct air capture of CO 2 . The polymers are synthesized with chloride counterions, followed by ion exchange to the bicarbonate ion, and tests for CO 2 capture capacity and stability under cyclic wet–dry conditions. The phosphonium polymer with methyl substituents [PVBT-MeP] demonstrates the highest CO 2 capture capacity at ≈510 µmol g⁻¹, attributed to minimal steric hindrance and stronger ion pairing with bicarbonate. However, oxidative degradation is detected by 31 P NMR spectroscopy after the moisture swing experiment, with the appearance of a phosphine oxide peak at 61.28 ppm, which indicates phosphorus oxidation as the primary degradation pathway. In contrast, the ammonium polymer with butyl substituents [PVBT-BuN] exhibits the highest stability, showing no degradation over five moisture swing cycles. Additional stability experiments in 0.5 m KHCO 3 solutions reveal no degradation for any PIL, suggesting that oxidative degradation is driven by dynamic acid-base reactions during the moisture swing cycles in the air. Furthermore, these findings reveal the potential of phosphonium-based PILs for moisture-swing direct air capture, achieving high capacity while highlighting the need for optimized stability through counterion and structural design.
Benchmarking anion-exchange membranes for electrocatalytic carbon monoxide reduction
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Impact of anion-exchange membrane degradation on long-term CO 2 electrolysis to ethylene
Electrochemical CO 2 reduction (eCO2R) to ethylene offers a unique opportunity to diversify domestic supply chains for chemical manufacturing. Large-scale deployment of eCO2R to ethylene reactors is currently limited by low energy efficiencies and poor durability. Herein, we demonstrate >100 h of continuous electrolysis at an industrially relevant current density of 200 mA cm −2 in a 25 cm 2 geometric area zero-gap reactor with a full-cell voltage <3.1 V and ethylene Faradaic efficiency >30%. Incorporating expanded polytetrafluoroethylene (PTFE)-supported electrodes into zero-gap reactors allows for durable electrode catalysts that are resistant to flooding, and this enables wider ranges of operating parameters not typically accessible in CO 2 electrolysis. Finally, we identify membrane degradation, evidenced by a loss of membrane ion-exchange capacity, as the leading cause of performance loss over 144 h of electrolysis.
Quaternized Tröger’s base polymer with crown ether unit for alkaline stable anion exchange membranes
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Optimizing the PTFE wetproofing of nickel porous transport layers for anion exchange membrane water electrolyzers
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