Perfluorosulfonate Ionomer Research Articles

Coupled cation–electron transfer at the Pt(111)/perfluoro-sulfonic acid ionomer interface and its impact on the oxygen reduction reaction kinetics

Coupled cation–electron transfer at the Pt(111)/perfluoro-sulfonic acid ionomer interface and its impact on the oxygen reduction reaction kinetics

Effect of Substituent in Phosphonic Acid on Anion Adsorption and Oxygen Reduction Reaction Activity

Acid anions affect Pt’s oxygen reduction reaction (ORR) activity. For weakly solvated anions like SO4 2- and H2PO4 -, they could adsorb onto Pt and block active sites for O2 adsorption, leading to lower ORR activity than that of nonspecifically or weakly adsorbed F- and ClO4 - anions 1. In low temperature proton exchange membrane fuel cells (PEMFCs) (60-80 °C), where the acid is perfluorinated sulfonic acid (PFSA) polymer, the adsorption of the terminal sulfonate anions (-SO3 -) suppresses ORR activity, and it was also found that the functional group adjacent to the sulfonate affects the anion adsorption and its effect on ORR activity 2,3. In high temperature PEMFCs (120-200 °C), where the acid could be phosphoric acid or phosphonated polymer 4–7, it is unclear yet how the adjacent organic group in those phosphonated polymers affect the terminal phosphonate group’s interaction with Pt and ORR activity. In this work, we select several low-molecular-weight organic phosphonic acids (R-PAs) as model molecules to study their interaction with Pt and the effect on ORR. With density function theory (DFT) simulation, we compare the binding strength of these organic phosphonic acids and their effect on ORR activity to H3PO4. At the same time, we use Pt disk electrode to study the adsorption/desorption behavior of the H, O, and anion species, with diluted acid solutions. By comparing the simulation and experiment results, we found that the electronic and steric effect contribute together to the reaction site number and the site’s reactivity, which provides useful information to address the acid poisoning issue in HT-PEMFCs. Reference (1) Kamat, G. A.; Zamora Zeledón, J. A.; Gunasooriya, G. T. K. K.; Dull, S. M.; Perryman, J. T.; Nørskov, J. K.; Stevens, M. B.; Jaramillo, T. F. Acid Anion Electrolyte Effects on Platinum for Oxygen and Hydrogen Electrocatalysis. Commun Chem 2022, 5 (1). https://doi.org/10.1038/s42004-022-00635-1.(2) Kodama, K.; Motobayashi, K.; Shinohara, A.; Hasegawa, N.; Kudo, K.; Jinnouchi, R.; Osawa, M.; Morimoto, Y. Effect of the Side-Chain Structure of Perfluoro-Sulfonic Acid Ionomers on the Oxygen Reduction Reaction on the Surface of Pt. ACS Catal 2018, 8 (1), 694–700. https://doi.org/10.1021/acscatal.7b03571.(3) Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts. J Electrochem Soc 2014, 161 (14), F1481–F1488. https://doi.org/10.1149/2.0921414jes.(4) Sun, X.; Guan, J.; Wang, X.; Li, X.; Zheng, J.; Li, S.; Zhang, S. Phosphonated Ionomers of Intrinsic Microporosity with Partially Ordered Structure for High-Temperature Proton Exchange Membrane Fuel Cells. ACS Cent Sci 2023, 9 (4), 733–741. https://doi.org/10.1021/acscentsci.3c00146.(5) Atanasov, V.; Lee, A. S.; Park, E. J.; Maurya, S.; Baca, E. D.; Fujimoto, C.; Hibbs, M.; Matanovic, I.; Kerres, J.; Kim, Y. S. Synergistically Integrated Phosphonated Poly(Pentafluorostyrene) for Fuel Cells. Nat Mater 2021, 20 (3), 370–377. https://doi.org/10.1038/s41563-020-00841-z.(6) Tang, H.; Gao, J.; Wang, Y.; Li, N.; Geng, K. Phosphoric-Acid Retention in High-Temperature Proton-Exchange Membranes. Chemistry - A European Journal 2022, 28 (70). https://doi.org/10.1002/chem.202202064.(7) Tang, H.; Geng, K.; Hu, Y.; Li, N. Synthesis and Properties of Phosphonated Polysulfones for Durable High-Temperature Proton Exchange Membranes Fuel Cell. J Memb Sci 2020, 605. https://doi.org/10.1016/j.memsci.2020.118107.

High protonic resistance of hydrocarbon-based cathodes in PEM fuel cells under low humidity conditions: Origin, implication, and mitigation

Hydrocarbon-based electrodes for proton-exchange membrane fuel cells face challenges in closing the performance gap with electrodes based on perfluorosulfonic acid ionomers, particularly under low humidity conditions. Alongside increased oxygen transport resistance and higher kinetic-induced overpotentials, the protonic resistance of these fluorine-free electrodes is the primary hurdle to improved performance. This study systematically investigates the origin and impact of the cathode protonic resistance on fuel cell performance, utilizing sulfonated phenylated polyphenylenes as hydrocarbon ionomers. Electrochemical characterization at low relative humidity (≤50 %) reveal a high protonic resistance arising from both lower conductivity of the hydrocarbon thin film compared to the bulk membrane and increased cathode tortuosity at a gas transport-optimized ionomer to carbon (I/C) ratio of 0.2. The poor protonic resistance at low relative humidities leads to a non-homogeneous current distribution across the thickness of the cathode electrode, resulting in lower catalyst utilization. To address this issue, reducing the thickness of the cathode CL while maintaining a constant Pt loading (i.e., increasing the Pt on carbon ratio) significantly reduces protonic resistance. This improvement compensates for the kinetic disadvantages of highly loaded carbon particles and results in a considerable performance increase by 40 % at 0.75 V under low relative humidities.

Gas Transport Resistance of Hydrocarbon-Based Catalyst Layers in Proton-Exchange Membrane Fuel Cells

Recent developments in hydrocarbon-based proton exchange membrane fuel cells have significantly narrowed the performance gap compared to state-of-the-art cells using perfluorosulfonic acid ionomers (PFSA). However, balancing protonic resistance and gas transport resistance in the catalyst layer remains a challenge at low humidity. This study investigates gas transport resistance and its components in sulfonated phenylated polyphenylene-based catalyst layers using various limiting current methods. Results show that increasing the dry ionomer to carbon (I/C) ratio from 0.2 to 0.4, a measure to catch up with protonic resistance of PFSA-based catalyst layers, significantly increases gas transport resistance in the cathode catalyst layer by 28 %. The data suggest a strong correlation between local gas transport resistance and IEC. A high IEC is beneficial for the gas transport through the ionomer film. However, at low ionomer volume fractions the local gas transport resistance is dominated by the I/C independent interfacial resistance. Furthermore, a low IEC hydrocarbon ionomer, such as Pemion® PP1-HNN4–00-X (IEC = 2.5 meq g−1), not only exhibits a beneficial interfacial resistance, but also suppresses excessive ionomer swelling, which typically occurs during operating conditions where liquid water is forming.

Study on ammonia transport and separation in Aquivion® perfluoro sulfonated acid membranes

The present study reports the results of a series of sorption and permeation tests of pure ammonia as well as nitrogen and hydrogen carried out on Aquivion C87-05 (short-side chain perfluoro sulfonic acid ionomer). Such material is indeed of interest for possible applications in sustainable processes for ammonia production, either as base material for polymer electrolyte membranes in low-temperature electrochemical ammonia synthesis or as a membrane for effective product separation.NH3, N2, and H2 permeation tests are performed at different temperatures (20, 35, and 50 °C) and both in dry and humid conditions (R.H. up to 80%), aiming to assess the influence of these parameters on the resulting permeabilities, while ammonia sorption is inspected at the same temperatures, and pressures up to near saturation conditions.Pure ammonia permeability reached outstanding values around 7000 Barrer in dry Aquivion membranes, revealing an increasing trend with upstream pressure, while it decreased with temperature. The same behavior is recorded for NH3 solubility, indicating that sorption drives the ammonia transport through the membrane.The obtained separation performances are found to be significantly better than those of other polymeric membranes proposed for the same separations, as compared to a permeability-selectivity plot.

Influence of Sidechain Length in Perfluoro-Sulfonic Acid Ionomer on Electrode Slurry Interactions and Finalized Microstructure in the Polymer Electrolyte Fuel Cells

Polymer electrolyte fuel cells (PEFCs) have emerged as one of the most promising next-generation energy devices for both passenger-owned and heavy-duty vehicles due to their high energy efficiency, low emissions, and quiet operation. However, the performance of the fuel cell electrode is often limited by the strong specific adsorption of long sidechain (LSC) perfluoro-sulfonic acid (PFSA) ionomer onto the platinum (Pt) catalyst2, which results in a decrease in the electrocatalytic activity1 as well as increase oxygen mass transport resistenace at the MEA level. To address this issue, a short sidechain (SSC) ionomer has been developed, which has been found to exhibit excellent efficiency over LSC ionomer3 The reduced specific adsorption of SSC ionomer onto the Pt catalyst results in a higher available surface area for the electrochemical reaction, which improves the overall fuel cell performance. The sidechain length of ionomers plays a crucial role in determining the overall cell performance4 however, due to the differences between them, the interactions among slurry components are not yet fully understood.Unlike the previous literatures, we investigates the details of ionomer sidechain length and its impact on the interaction among slurry components and resulting electrode microstructure, through a comparative analysis of LSC and SSC ionomers.5 Our hypothesis propose that the physical interactions between components are considerably impacted by the sidechains with a specific emphasis on the mobility and ion-pair association in the slurry. To probe the influence of ionomer sidechains, we conducted a thorough investigation wherein incrementally varied its concentration from 0 to 1.5 mmolSO3-gC -1, at intervals of 0.3 mmolSO3-gC -1. The main purpose of this evaluation was to observe the evolution of particle aggregation according to the correlation between adsorbed ionomer and free ionomer in electrode slurry. Drawing from the U-shaped viscosity profile obtained through rheological measurements, we propose an optimized ionomer concentration of 0.6 mmolSO3-gC -1 for the SSC ionomer-based slurry and 0.9 mmolSO3-gC -1 for the LSC ionomer-based slurry. To characterize the microstructure of the as-prepared electrode, we employed scanning electron microscopy (SEM) and confocal microscopy, with a focus on particle agglomeration and the homogeneous ionomer distribution. Finally, the electrochemical analysis was performed on the fabricated membrane electrode assembly (MEA) in a 25 cm² single cell for a cathode Pt loading of 0.1 mgPtcm⁻². As a result, the optimized SSC ionomer-based electrode exhibited low local O₂ transport resistance and high Pt utilization, leading to over a 40 % enhancement in fuel cell performance at 0.6 V with a high proton accessibility value above 0.85 when compared to the optimized LSC ionomer-based electrode. This study highlights the crucial importance of understanding the effects of ionomer sidechain length on electrode slurry interactions and microstructure and establishes a significant correlation between them. Our findings contribute to the ongoing development of high-performance PEFCs, offering valuable insights into optimizing electrode composition and structure for enhanced fuel cell performance.(1) Ahn, C.-Y.; Park, J. E.; Kim, S.; Kim, O.-H.; Hwang, W.; Her, M.; Kang, S. Y.; Park, S.; Kwon, O. J.; Park, H. S. Differences in the electrochemical performance of Pt-based catalysts used for polymer electrolyte membrane fuel cells in liquid half-and full-cells. Chemical Reviews 2021, 121 (24), 15075-15140.(2)Kodama, K.; Motobayashi, K.; Shinohara, A.; Hasegawa, N.; Kudo, K.; Jinnouchi, R.; Osawa, M.; Morimoto, Y. Effect of the side-chain structure of perfluoro-sulfonic acid ionomers on the oxygen reduction reaction on the surface of Pt. ACS Catalysis 2018, 8 (1), 694-700. (2) Garsany, Y.; Atkinson, R. W.; Sassin, M. B.; Hjelm, R. M.; (3) Gould, B. D.; Swider-Lyons, K. E. Improving PEMFC Performance Using Short-Side-Chain Low-Equivalent-Weight PFSA Ionomer in the Cathode Catalyst Layer. Journal of The Electrochemical Society 2018, 165 (5), F381-F391.(4) Ramaswamy, N.; Kumaraguru, S.; Koestner, R.; Fuller, T.; Gu, W.; Kariuki, N.; Myers, D.; Dudenas, P. J.; Kusoglu, A. Editors’ Choice—Ionomer Side Chain Length and Equivalent Weight Impact on High Current Density Transport Resistances in PEMFC Cathodes. Journal of The Electrochemical Society 2021, 168 (2), 024518.(5) Mauritz, K. A.; Moore, R. B. State of Understanding of Nafion. Chemical Reviews 2004, 104 (10), 4535-4586. DOI: 10.1021/cr0207123.

High-performance and durable membrane electrode assemblies based on CeO2 and ePTFE double-reinforcement strategy for proton exchange membrane fuel cells operating at elevated temperatures

The membrane electrode assemblies (MEAs) play a decisive role in operating conditions and lifetime of fuel cell. In this study, MEAs that could work stably at elevated temperatures were prepared. With this method, a short-side chain perfluorosulfonic acid ionomer coating with CeO2 nanoparticles and two layers of expanded polytetrafluoroethylene reinforcement, to be used as a proton exchange membrane, was directly deposited between the cathode and anode gas diffusion electrodes, forming a double-reinforced integrated MEA. The effects of CeO2 doping amount on performance and other electrochemical properties of MEAs were systematically studied. Under the coupling effect of the water-retention and non-proton-conducting properties of CeO2, the 0.5 wt% CeO2-doped MEA (MEA-S0.5) had optimal performance above 100 °C and under low relative humidity (RH) conditions. At 120 °C and 30% RH, MEA-S0.5 exhibited peak power density of 0.460 W cm−2 (H2/air operation, 100 kPa), which was about 1.28 times that of MEA without CeO2 doping (MEA-S0). Furthermore, CeO2 effectively enhanced the durability of the MEA. Compared with MEA-S0, MEA-S0.5 did not exhibit significant degradation in output power, H2 crossover, or proton conductivity in the 100-h open-circuit voltage-holding test. This work paves the way for developing high-performance, durable MEAs that are suitable for elevated temperatures.

Substitution of the Nafion® Ionomer with Hydroxypropyl Methylcellulose for Proton Exchange Membrane Water Electrolyzer

The use of green hydrogen as a clean energy carrier has become an essential method of storing renewable energy instead of fossil fuels because of environmental concerns[1,2]. Proton exchange membrane water electrolysis (PEMWE) is one of several methods of producing green hydrogen. A perfluorosulfonic acid ionomer called Nafion® was typically used as a binder in PEMWE for many years. It has excellent chemical stability and high ionic conductivity, but it is expensive and has negative environmental effects [3]. It is therefore necessary to investigate new binders for the anode of PEMWE.In this study, we present a new electrode manufacturing method using hydroxypropyl methylcellulose (HPMC) binder and demonstrate that HPMC binder can be used sufficiently instead of traditional Nafion® ionomer through single-cell evaluation under PEMWE conditions. Although it has the disadvantage of low proton conductivity, HPMC is cost-effective and eco-friendly. In the case of the PEMWE anode, because water moves into the cell, water can take over the role of hydrogen ion transport instead of the HPMC binder. By the electrode’s interfacial stability test, it was discovered that the HPMC electrode’s form was preserved for 24 hours without any peeling. Further, it can be seen that there is no significant difference in PEMWE performance even if an HPMC binder with relatively low ionic conductivity is used. Additionally, it was established that each electrode demonstrated a low degradation (less than 0.3 mV h-1) in the subsequent 72 h durability test. The proposed affordable new binder HPMC can aid the development of a new electrode and a cost-effective PEMWE system.

Aging gracefully? Investigating iridium oxide ink's impact on microstructure, catalyst/ionomer interface, and PEMWE performance

In this study, we conducted a thorough investigation of the impact of aging iridium oxide (IrO2) perfluorosulfonic acid ionomer ink for up to 14 days on the properties of the ink and the resulting catalyst layers. We examined ink properties, such as zeta potential, dynamic light scattering (DLS), density, surface tension, and rheology, as functions of ink aging time. To evaluate the microstructure and catalyst/ionomer interface, we employed transmission electron microscopy (TEM), X-ray scattering, and X-ray photoelectron spectroscopy (XPS) techniques. Furthermore, we assessed the effect of ink aging on the performance of proton exchange membrane water electrolyzers (PEMWEs). Our findings reveal that most ink properties remain stable for 14 days. The variations in PEMWE cell performance are minimal, and no clear trend is observed in relation to ink aging time. This study demonstrates that the effects of aging the inks for 14 days on ink properties, catalyst layer structure, catalyst/ionomer interface, and PEMWE performance are negligible, indicating a substantial time window after ink preparation without any significant changes in its properties. These insights provide crucial guidance for the commercial production and coating processes of ink, which is necessary for scaling up PEM technologies to meet future demand.

Protection Against Absorption Passivation on Platinum by a Nitrogen-Doped Carbon Shell for Enhanced Oxygen Reduction Reaction.

In polymer electrolyte type fuel cells, the platinum-based catalysts are applied for the oxygen reduction reaction. However, the specific adsorption from the sulfo group in perfluorosulfonic acid ionomers has been considered to passivate the active sites of the platinum. Herein, we present platinum catalysts covered by an ultrathin two-dimensional nitrogen-doped carbon shell (CNx) layer to protect the platinum from the specific adsorption of perfluorosulfonic acid ionomers. Such coated catalysts were obtained by the facile polydopamine coating method, which is available to tune the thickness of the carbon shell by tuning the polymerization time. The coated catalysts that possess a CNx with a thickness of 1.5 nm demonstrated superior ORR activity and comparable oxygen diffusivity when compared to the commercial Pt/C. These results were supported by the changes in the electronic statements observed in the X-ray photoelectron spectroscopy (XPS) and CO stripping analyses. Furthermore, the oxygen coverage, CO displacement charge, and operando X-ray absorption spectroscopy (XAS) tests were employed to identify the protection effect of CNx in coated catalysts compared with the Pt/C catalysts. In summary, the CNx could not only suppress the oxide species generation but also prevent the specific adsorption of the sulfo group in the ionomer.

On-body hypoxia monitor based on lactate biosensors with a tunable concentration range

We report on a noninvasive hypoxia monitor based on a biosensor linearly responding to lactate through its whole concentration range in human sweat. The biosensor is designed with an additional perfluorosulfonated ionomer (Nafion analogue) membrane acting as a diffusion barrier for lactate due to its intrinsic negative charge. The resulting biosensor linearly responds to lactate in the range from 1 to 100 mM and displays significantly improved operational stability, maintaining its initial response during 3 h in human sweat flow. Thus, the elaborated monitor has been validated through on-body continuous sweat analysis during exhaustive physical exercise. In contrast to periodic sweat sampling, the elaborated monitor allows recording of the true extremes of sweat lactate, which are of particular importance for diagnostics.

Deconvoluting charge-transfer, mass transfer, and ohmic resistances in phosphonic acid–sulfonic acid ionomer binders used in electrochemical hydrogen pumps

This work reveals how electrode binders affect reaction kinetics, ionic conductivity, and gas transport in electrochemical hydrogen pumps (EHPs). Using a blend of phosphonic acid and perfluorosulfonic acid ionomers as the electrode binder, an EHP was operated at 5 A cm−2.

Elucidating the impact of the ionomer equivalent weight on a platinum group metal‐free PEMFC cathode via oxygen limiting current

AbstractLeveraging the interactions between ionomer and catalyst can increase the performance of proton exchange membrane fuel cells. The impacts of the equivalent weight (EW) of perfluorosulfonic acid–based ionomers on the platinum group metal‐free electrode structure and fuel cell performance have not been fully explored. Four membrane electrode assemblies (MEAs) were prepared by using a commercial Fe–N–C catalyst, two perfluorosulfonic acid ionomers with different EWs, that is, Aquivion 720 (A720) and Nafion 1100 (N1100), and two ionomer‐to‐catalyst (I/C) ratios. The four MEAs were characterized to understand the impact of the ionomer EW and content on the capacitance, proton conductivity, and mass transport on the cathode. The mass transport resistance was measured for the first time using a new oxygen reduction reaction limiting current method enabling to couple the effects of oxygen diffusion with liquid water generation. Low EW ionomer combined with a moderate I/C results in improved performance due to its enhanced proton conductivity. However, when used at high I/C, it can cause severe water flooding at high current density due to the enhanced liquid water uptake, especially at high relative humidity, resulting in lower catalyst utilization and higher mass transport resistance.

Dependence of oxygen transport properties of catalyst layers for polymer electrolyte fuel cells on the fabrication process

Herein, we report the oxygen transport phenomenon in the cathode catalyst layer of polymer electrolyte fuel cells. The oxygen transport resistance in the catalyst layer depended on the hot-pressing temperature of the fabrication procedure, suggesting morphological changes in the perfluorosulfonic acid ionomer of the catalyst layers. This work aims to highlight the importance of the manufacturing process in the oxygen transport properties of the catalyst layer.

Molecular dynamics simulation of inhomogeneous density distribution mechanism of Ultra-Thin perfluoro sulfonic acid ionomer films on Triple-phase interface of PEM fuel cells

The proton exchange membrane (PEM) fuel cell is a clean power generation component with high energy conversion rate and high energy density. The triple-phase interfaces of catalytic layer are where the electrochemical reaction occurs in proton exchange membrane (PEM) fuel cell, and its distribution directly affect the reactivity. The triple-phase interface is a nano-thick perfluorosul-fonic acid ionomer (PFSA) film that covers the catalyst particles. When the density of the ultra-thin PFSA film is not uniform, the gas transport resistance increases significantly, which is not conducive to the progress of reaction. However, ultra-thin PFSA film will have inhomogeneous density distribution due to the influence of forming process. Therefore, how to design the process to improve density distribution of ultra-thin films is an urgent problem. Molecular dynamics simulation model is built to study the influence of manufacturing process on inhomogeneous distribution of ultra-thin PFSA film, and the microscopic mechanism is revealed.

Operando X-Ray Absorption Spectroscopic Study on Influence of Specific Adsorption of Sulfo Group in Perfluorosulfonic Acid Ionomer Towards ORR Activity of Pt/C Catalyst

Polymer electrolyte fuel cells (PEFCs) are clean energy devices with polymer electrolytes and are expected to play an important role in the development of a global renewable energy system and a pure hydrogen energy society in the future. PEFCs have already been applied for small-scale energy systems such as fuel cell vehicles (FCVs). Pt-based catalysts are basically used due to the relatively inefficient reaction kinetics and catalyst degradation under strong acidic conditions during the oxygen reduction reaction (ORR). However, there are still many difficulties in realizing acceptable cost-effective FCVs. It is known that the ORR activity of Pt-based catalysts is reduced by specific adsorption of anionic species. Perfluorosulfonic acid ionomers such as Nafion® are commonly included in the catalyst layers of PEFCs to provide protonic pathways for promoting the ORR1. However, direct observation of anion adsorption on practical Pt nanoparticle/C catalysts for perfluorosulfonic acid ionomers using X-ray absorption spectroscopy (XAS) still has less report. In this study, to achieve specific adsorption over a higher potential range that is at least equal to the ORR active potential (around 0.90 V vs. RHE), operando XAS measurements were performed; the electronic status and local structural change of Pt atoms induced by the specific adsorption of anions at any potential were observed2.Pt/C (29.1 wt.%; TEC10V30E) catalyst supported was purchased from TKK. Nafion® solution was employed to prepare Pt/C catalyst ink with I/C ranging from 0.0 to 1.0. And the amount of Pt/C was adjusted to form a 20 µgcarbon cm-2 catalyst layer after dropping 10 μL on a glassy carbon RDE. The electrochemical cell was constructed using a model electrode fabricated in the working electrode, a Pt mesh for the counter electrode, a reversible hydrogen electrode for the reference electrode, and 0.1 M HClO4 aq for the electrolyte. operando XAS measurement of Pt L-edge was carried out in SPring-8 (Japan).The specific activity decreased as the I/C ratio increased from 0.0 to 0.20. We utilized many methods to evaluate the adsorption species separately, including the measurements of ECSA and oxygen coverage, CO stripping voltammetry, operando X-ray absorption fine structure, and analysis of 5d orbital vacancy. The ECSA and oxygen coverage did not change with increasing ionomer content, indicating that the Pt/C catalyst activity was affected by other adsorption species. A comparison of the CO displacement charge and 5d orbital vacancies of the Pt/C catalysts with I/C = 0.0 and 1.0 suggests that the ionomer-specific adsorption increases when the I/C ratio of the Pt/C catalyst is 1.0; active sites on the surface of the Pt/C catalyst are occupied, resulting in lower catalyst activity. Acknowledgment This work was supported by the project (JPNP20003) and a NEDO FC-Platform project commissioned by the New Energy and Industrial Technology Development Organization (NEDO).

Cellulose Nanocrystals Crosslinked with Sulfosuccinic Acid as Sustainable Proton Exchange Membranes for Electrochemical Energy Applications.

Nanocellulose is a sustainable material which holds promise for many energy-related applications. Here, nanocrystalline cellulose is used to prepare proton exchange membranes (PEMs). Normally, this nanomaterial is highly dispersible in water, preventing its use as an ionomer in many electrochemical applications. To solve this, we utilized a sulfonic acid crosslinker to simultaneously improve the mechanical robustness, water-stability, and proton conductivity (by introducing -SO3−H+ functional groups). The optimization of the proportion of crosslinker used and the crosslinking reaction time resulted in enhanced proton conductivity up to 15 mS/cm (in the fully hydrated state, at 120 °C). Considering the many advantages, we believe that nanocellulose can act as a sustainable and low-cost alternative to conventional, ecologically problematic, perfluorosulfonic acid ionomers for applications in, e. fuel cells and electrolyzers.

Electro-Sorption of Hydrogen by Platinum, Palladium and Bimetallic Pt-Pd Nanoelectrode Arrays Synthesized by Pulsed Laser Ablation.

Sustainable and renewable production of hydrogen by water electrolysers is expected to be one of the most promising methods to satisfy the ever-growing demand for renewable energy production and storage. Hydrogen evolution reaction in alkaline electrolyte is still challenging due to its slow kinetic properties. This study proposes new nanoelectrode arrays for high Faradaic efficiency of the electro-sorption reaction of hydrogen in an alkaline electrolyte. A comparative study of the nanoelectrode arrays, consisting of platinum or palladium or bimetallic nanoparticles (NPs) Pt80Pd20 (wt.%), obtained by nanosecond pulsed laser ablation in aqueous environment, casted onto graphene paper, is proposed. The effects of thin films of perfluoro-sulfonic ionomer on the material morphology, nanoparticles dispersion, and electrochemical performance have been investigated. The NPs-GP systems have been characterized by field emission scanning electron microscopy, Rutherford backscattering spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, cyclic voltammetry, and galvanostatic charge-discharge cycles. Faradaic efficiency up to 86.6% and hydrogen storage capacity up to 6 wt.% have been obtained by the Pt-ionomer and Pd/Pt80Pd20 systems, respectively.

Ultrastable Lactate Biosensor Linearly Responding in Whole Sweat for Noninvasive Monitoring of Hypoxia.

We report on the lactate biosensor with linear calibration range from 0.5 to 100 mM, which encircles possible levels of this metabolite concentration in both human sweat and blood. The linear calibration range at high analyte concentrations, which exceeds the Michaelis constant of lactate oxidase by several orders of magnitude, is provided by an additional perfluorosulfonated ionomer diffusion membrane. In contrast to the known lactate biosensors, which retain their response within less than a couple of hours, the reported system displays 100% response for dozens of hours even upon high analyte concentrations. The biosensors with an additional diffusion-limiting membrane have been validated for lactate detection both in human blood serum and in undiluted human sweat shortly after its secretion. Both linear response in the entire range of blood and sweat lactate concentrations and ultrahigh operational stability would provide the use of the elaborated biosensor in wearable devices for the monitoring of hypoxia.

Mathematical Description of the Increase in Selectivity of an Anion-Exchange Membrane Due to Its Modification with a Perfluorosulfonated Ionomer

In this paper, we simulate the changes in the structure and transport properties of an anion-exchange membrane (CJMA-7, Hefei Chemjoy Polymer Materials Co. Ltd., China) caused by its modification with a perfluorosulfonated ionomer (PFSI). The modification was made in several stages and included keeping the membrane at a low temperature, applying a PFSI solution on its surface, and, subsequently, drying it at an elevated temperature. We applied the known microheterogeneous model with some new amendments to simulate each stage of the membrane modification. It has been shown that the PFSI film formed on the membrane-substrate does not affect significantly its properties due to the small thickness of the film (≈4 µm) and similar properties of the film and substrate. The main effect is caused by the fact that PFSI material “clogs” the macropores of the CJMA-7 membrane, thereby, blocking the transport of coions through the membrane. In this case, the membrane microporous gel phase, which exhibits a high selectivity to counterions, remains the primary pathway for both counterions and coions. Due to the above modification of the CJMA-7 membrane, the coion (Na+) transport number in the membrane equilibrated with 1 M NaCl solution decreased from 0.11 to 0.03. Thus, the modified membrane became comparable in its transport characteristics with more expensive IEMs available on the market.