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At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Modeling Water Electrolysis in Bipolar Membranes

Bipolar membranes (BPMs) have proven useful in numerous electrochemical energy conversion and storage applications, including fuel cells and electrolyzers. However, water dissociation in bipolar membrane electrolysis cells (BPMECs) is a complicated phenomenon that occurs via several different pathways. In this work, we develop a model based on the Poisson-Nernst-Planck system that includes a multistep water-dissociation mechanism to observe the fundamental processes that contribute to BPMEC performance. The model, which is validated to in-house experimental data, demonstrates that the junction potential is the most significant contributor to the total electrolysis voltage. We investigated the effects of water-dissociation catalysts and found that the optimal catalyst $p{K}_{a}$ depends on how the catalyst is integrated into the BPM (although values near 7 are typically best, in accordance with conventional wisdom). We also simulated the water content across the BPM and found that dry-out is not a significant issue when the membrane is in contact with liquid water on both sides. The species conservation approach taken here leads to a physical understanding of the system without using any fitting parameters.

25 ENERGY STORAGE↗
DOE OSTI2023

2023 American Society for Mass Spectrometry (ASMS) 71st Annual Conference on Mass Spectrometry and Allied Topics

Introduction (120 words max) Understanding metal-cluster chemistry occuring at solvent boundaries in the aqueous and organic phases has applications in environments from cellular processes to nuclear fuel reprocessing. Transport of metal ions at the boundaries from aqueous to organic phases involves forming a metal-ligand complex, and wherever the initial metal coordination environment is significantly different from the final one, the metal transitions through a series of transient species in passing from one phase to another. Here an investigation of the role of coordination in the chemistry of the transient species using gas-phase measurements that are free of solvent effects to better understand the binding of complexes of metals with triphenylphosphine chalcogenide ligands, examining metal-ligand homo- and hetero-dimers to better understand transient species. Methods (120 word max) Mass spectrometry and collision induced dissociation (CID) experiments were performed with a Bruker (Billerica, MA, USA) micrOTOF-Q II quadrupole time-of-flight mass spectrometer (QTOF) and Bruker amaZon speed ETD (ion trap). High resolution/high mass accuracy spectra were generated using the QTOF. External calibration was performed with Agilent (Santa Clara, CA, USA) ESI-L Low Concentration tuning mix. Both mass spectrometers were equipped with either the electrospray ionization source or nanospray sources. Metal samples were prepared between 40 – 60 uM of the metal-ligand complex in 25% water and 75% acetonitrile. Metal-ion clusters were isolated and subjected to collision induced dissociation. Density functional theory calculations were performed. Preliminary Data or Plenary Speakers Abstract (300 words max) Metal ion clusters with triphenylphosphine chalcogenide ligands were observed for group I metals with triphenylphosphine chalcogenide samples in the mass spectrum upon electrospray ionization. For each metal ligand complex of interest, the parent ion was isolated and collision induced dissociation fragmentation spectra were acquired. We observed clusters of group I metal with triphenylphosphine oxide, triphenyl phosphine sulfide, and triphenylphosphine selenide, with homodimers and heterodimer formation. In samples where the ligands were mixed, we observed mixed sodium ligand clusters at varying amounts. These mixed ligand clusters were fragmented. Metal clusters of mixed ligand dimers containing triphenylphosphine oxide showed preferential loss of the other ligand, either triphenylphosphine sulfide or triphenyl selenide. In samples with mixed triphenylphosphine sulfide and triphenylphosphine selenium ligands, sodium bound similarly between the ligands, and losses were more evenly split, showing loss ratio upon CID with losses of triphenylphosphine sulfide:triphenylphosphine selenide 43:57 ratio observed on CID. These results suggest that the oxide binds significantly more strongly than either the selenium or sulfur triphenylphosphine ligand, and the sulfur and selenium ligands are more evenly bound. Calculations were performed using density functional theory to calculate likely structures and bond energies between the group I metal and the ligands. Novel Aspect Novel analysis of sodium bound dimers with chalcogenide triphenylphosphine ligands were investigated using mass spectrometry and theoretical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Boosting the H 2 –D 2 Exchange Activity of Dilute Nanoporous Ti–Cu Catalysts through Oxidation–Reduction Cycle–Induced Restructuring

The use of nanoporous metals as catalysts has attracted significant interest in recent years. Their high-curvature, nanoscale ligaments provide not only high surface area but also a high density of undercoordinated step edge and kink sites. However, their long-term stability, especially at higher temperatures, is often limited by thermal coarsening and the associated loss of surface area. Herein, it is demonstrated that the nanoscale morphology of nanoporous Cu can be regenerated by applying oxidation/reduction cycles at 250 °C. Specifically, the morphological evolution and H 2 dissociation activity of hierarchical nanoporous Cu catalysts doped with Ti during structural rearrangement triggered by oxidative and reductive atmospheres at elevated temperatures are studied. In addition to coarsening of the structure at elevated temperatures, oxidation at 400 °C causes an expansion of the ligaments. Further, subsequent reduction at 400 °C leads to the formation of particles and a drop in the H 2 dissociation activity compared the fresh catalyst. However, performing the redox cycle at 250 °C reverses coarsening and boosts the H 2 dissociation activity for the hydrogen–deuterium (H 2 –D 2 ) reaction. Herein, the possibility to reverse coarsening is demonstrated, thereby mitigating the loss of activity frequently observed in nanoporous catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Half‐sandwich ruthenium complex with a very low overpotential and excellent activity for water oxidation under acidic conditions

Abstract Molecular catalysts are acknowledged for the ability to design reaction sites within well‐defined structures to achieve high catalytic activities. However, in many cases, molecular catalysts undergo structural changes to some other form(s), which are finally the real catalysts. Here, we report two half‐sandwich ruthenium complexes; [Ru([9]aneN3)(bpy)Cl] + 3 and [Ru([9]aneN3)(pic)OH 2 ] 2+ 4 , based on the macrocyclic 1,4,7‐triazacyclononane ([9]aneN3) ligand for water oxidation (WO). The two complexes have similar core but different ancillary ligands, which greatly affected their stability as well as activity for WO. Complex 3 retained high stability and excellent activity (turnover number [TON] = 1250) in chemical WO and first‐order reaction kinetics with respect to [Ce IV ] with a calculated rate constant ( k cat ) of 34.59 s −1 . Further, the complex demonstrated very low overpotential of ~210 mV in electrochemical WO. At an overpotential of only 400 mV, turnover frequency (TOF) of complex 3 was electrochemically estimated to be 131.2 s −1 . In contrast, complex 4 underwent picolinate ligand dissociation, as a deactivation pathway, to form the tri‐aqua derivative. Density functional theory (DFT) calculations are used to explain the dissociation mechanism of picolinate ligand in complex 4 , which happens through a stepwise dissociation mechanism.

Younus, Hussein A.↗
DOE OSTI2021

Rhodium Single–Atom Catalysts on Titania for Reverse Water Gas Shift Reaction Explored by First Principles Mechanistic Analysis and Compared to Nanoclusters

The thermocatalytic reduction of CO2 by H2 often proceeds via two competing reaction mechanisms—the reverse water gas shift reaction (rWGSR, CO2 + H2 ⇌ CO + H2O) and methanation (CO2 + 4H2 ⇌ CH4 + 2H2O). Atomically dispersed Rh1 catalysts on TiO2 show high selectivity toward the rWGSR compared with larger Rh nanoclusters, but the origin of this size-dependent selectivity has not been fully explained. Here we report density functional theory (DFT) calculations and microkinetic simulations that clarify the Rh1 active sites and rWGSR pathway on anatase TiO2(101), as well as the high rWGSR selectivity of Rh1 compared with supported Rhx (x = 2–8 atoms) nanoclusters. DFT-computed formation energies, vibrational frequency analysis, and microkinetic modeling suggest three plausible active sites: Rh1 on titania (Rh1/TiO2(101)), Rh1 with a nearby hydroxyl group (Rh1OH/TiO2(101)), and Rh1 near an oxygen vacancy at a three-fold coordinated site (Rh1 near O3cvac). Predicted turnover frequencies and apparent activation barriers for Rh1 indicate a faster reaction involving CO2 dissociation assisted by a support oxygen vacancy via Rh1 near O3cvac, as well as slower reactions involving Rh1OH/TiO2(101) or Rh1/TiO2(101) through a COOH intermediate. Furthermore, these Rh1 sites are selective toward CO rather than CH4 because of the weak adsorption of CO, large barrier for C-O bond dissociation, and the lack of nearby metal sites for H2 dissociation, in contrast to Rhx nanoclusters, including Rh2 dimers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Understanding the stability of a plastic‐degrading Rieske iron oxidoreductase system

Abstract Rieske oxygenases (ROs) are a diverse metalloenzyme class with growing potential in bioconversion and synthetic applications. We postulated that ROs are nonetheless underutilized because they are unstable. Terephthalate dioxygenase (TPA DO PDB ID 7Q05 ) is a structurally characterized heterohexameric α 3 β 3 RO that, with its cognate reductase (TPA RED ), catalyzes the first intracellular step of bacterial polyethylene terephthalate plastic bioconversion. Here, we showed that the heterologously expressed TPA DO /TPA RED system exhibits only ~300 total turnovers at its optimal pH and temperature. We investigated the thermal stability of the system and the unfolding pathway of TPA DO through a combination of biochemical and biophysical approaches. The system's activity is thermally limited by a melting temperature ( T m ) of 39.9°C for the monomeric TPA RED , while the independent T m of TPA DO is 50.8°C. Differential scanning calorimetry revealed a two‐step thermal decomposition pathway for TPA DO with T m values of 47.6 and 58.0°C (Δ H = 210 and 509 kcal mol −1 , respectively) for each step. Temperature‐dependent small‐angle x‐ray scattering and dynamic light scattering both detected heat‐induced dissociation of TPA DO subunits at 53.8°C, followed by higher‐temperature loss of tertiary structure that coincided with protein aggregation. The computed enthalpies of dissociation for the monomer interfaces were most congruent with a decomposition pathway initiated by β‐β interface dissociation, a pattern predicted to be widespread in ROs. As a strategy for enhancing TPA DO stability, we propose prioritizing the re‐engineering of the β subunit interfaces, with subsequent targeted improvements of the subunits.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Understanding how chemical structure affects ignition-delay-time $\phi$-sensitivity

$\phi$-sensitivity is the change in ignition delay time (IDT) with respect to the fuel-to-air equivalence ratio ($\phi$). High $\phi$-sensitivity is a desirable fuel property for applications in advanced compression ignition and multi-mode engine designs. Understanding how $\phi$-sensitivity depends on chemical structure is essential for selecting promising biofuels from the ever-growing list of proposed candidates. Here, we investigate the effect of chemical structure on $\phi$-sensitivity with experiment, simulation, and theory. Experimental Advanced Fuel Ignition Delay Analyzer (AFIDA) measurements for 2,4-dimethylpentane and diisopropyl ether provide evidence that branching and functional groups strongly impact $\phi$-sensitivity. Further insights into this dependence are obtained with 0-D kinetic simulations with existing mechanisms for n-pentane, diethyl ether, 3-pentanone, n-heptane, 2-methylhexane, 2,4-dimethylpentane, and 2,2,3-trimethylbutane. Quantum mechanical (QM) G4 calculations of low-temperature reactions help explain the observed experimental and simulation trends. Specifically, these QM calculations provide theoretical estimates of the ketohydroperoxide (KHP) dissociation rates, the HO 2 formation rates from peroxy radical (ROO), and the “cross-over” temperatures, i.e., the temperature at which ROO dissociation is favored compared to hydroperoxyl radical (QOOH) formation. Each of these reaction rates is compared to the n-alkane reference point to determine the impact of branching and different functional groups. Although kinetic mechanisms typically assume that KHP dissociation rates are invariant of chemical environment, our QM results suggest that this rate can span a range of roughly two orders of magnitude. We also discuss the importance of including the peroxy-hydroperoxy (OO-OOH) hydrogen transfer reaction for branched ethers. Finally, the insights gained assist in proposing a highly $\phi$-sensitive compound, namely, isopropyl propyl ether.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Probing the surface chemistry for reverse water gas shift reaction on Pt(1 1 1) using ambient pressure X-ray photoelectron spectroscopy

Using ambient pressure XPS (APXPS), we explored carbon dioxide (CO 2 ) adsorption and CO 2 hydrogenation on Pt(1 1 1) single crystal surface to observe the activation of CO 2 and the subsequent reaction mechanism. In pure CO 2 , we observed CO adsorbates and adsorbed oxygen on Pt(1 1 1) derived from CO 2 dissociation at room temperature. The introduction of H 2 (at a pressure ratio of 1:1 (H 2 :CO 2 )) increased the production of CO across all temperatures by facilitating the removal of surface oxygen. As a consequence, the surface could expose sites that could then be utilized for producing CO. Under these conditions, the reverse water–gas shift (RWGS) reaction was observed starting at 300 °C. At higher H 2 partial pressure (10:1 (H 2 :CO 2 )), the RWGS reaction initiated at a lower temperature of 200 °C and continued to enhance the conversion of CO 2 with increasing temperatures. Our results revealed that CO 2 was activated on a clean Pt(1 1 1) surface through the dissociation mechanism to form adsorbed CO and O at room temperature and at elevated temperatures. Introducing H 2 facilitated the RWGS as adsorbed oxygen was consumed continuously to form H 2 O, and adsorbed CO desorbed from the surface at elevated temperatures. This work clearly provides direct experimental evidence for the surface chemistry of CO 2 dissociation and demonstrates how hydrogen impacts the RWGS reaction on a platinum surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hydrogen activation by rhodium under the cover of a copper oxide thin film

Here, the activation of reactants by catalytically active metal sites at metal-oxide interfaces is important for understanding the effect of metal-support interactions on nanoparticle catalysts and for tuning activity and selectivity. Using a combined experimental and theoretical approach, we studied the activation of H 2 and the effect of CO poisoning on isolated Rh atoms completely or partially covered by a copper oxide (Cu 2 O) thin film. Temperature-programmed desorption (TPD) experiments conducted in ultra-high vacuum (UHV) show that neither a partially nor a fully oxidized Cu 2 O layer grown on a Rh/Cu(111) single-atom alloy can activate hydrogen in UHV. However, in situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments performed at elevated H 2 pressures reveal that Rh significantly accelerates the reduction of these Cu 2 O thin films by hydrogen. Remarkably, the fastest reduction rate is observed for the fully oxidized sample with all Rh sites covered by Cu 2 O. Both TPD and AP-XPS data demonstrate that these covered Rh sites are inaccessible to CO, indicating that Rh under Cu 2 O is active for H 2 dissociation but cannot be poisoned by CO. In contrast, an incomplete oxide film leaves some of the Rh sites exposed and accessible to CO, and hence prone to CO poisoning. Density functional theory calculations demonstrate that unlike many reactions in which hydrogen activation is rate limiting, the rate-determining step in the dissociation of H 2 on thin-film Cu 2 O with Rh underneath is the adsorption of H 2 on the buried Rh site, and once adsorbed, the dissociation of H 2 is barrierless. These calculations also explain why H 2 can only be activated at higher pressures. Together, these results highlight how different the reactivity of atomically dispersed Rh in Cu can be depending on its accessibility through the oxide layer, providing a way to engineer Rh sites that are active for hydrogen activation but resilient to CO poisoning.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Insights into the methanol synthesis mechanism via CO 2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio

In this study, we evaluated aspects of the CO 2 hydrogenation mechanism, correlating structure-activity relationships of Cu-ZnO-ZrO 2 catalysts prepared by one-pot surfactant-assisted co-precipitation with different surfactant ratios. Identifying the CO 2 hydrogenation pathway intermediates is key to controlling the reaction selectivity. Experimental evidence shows that the CO 2 is dissociating into CO* and O* onto the surface of the Cu-ZnO-ZrO 2 catalyst. The adsorption and dissociation of CO2 were evidenced by a combination of in situ ambient-pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Fourier Transform Infrared Spectroscopy (FTIR) with a transmission cell. AP-XPS showed that the catalysts are composed of a Cu 2+ , Zr 3+ , and Zr 4+ mixture and two kinds of Zn 2+ species. After the H 2 reduction process, only Cu 2+ was reduced to Cu0. The Zn and Zr species were oxidized by the dissociated O* species. In situ transmission FTIR showed that CO was adsorbed onto the Cu+/0 sites. The catalyst with the higher surfactant molar ratio exhibited the highest CO 2 conversion close to the equilibrium conversion, as well as a good methanol formation rate.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Helium interaction with solutes and impurities in neutron-irradiated nanostructured ferritic alloys: A first principles study

Density functional theory calculations are performed to explore the binding between He and alloying solutes, impurities, and transmutation products expected in neutron irradiated nanostructured ferritic alloys (NFAs), here 14YWT is taken as an example. Elements that exhibit significant binding (attraction) with an interstitial He are Y (binding energy = 0.46 eV), Mg (0.32), O (0.33), Ti (0.16), and C (0.15). Those that provide significant binding to a substitutional He are O (1.44), Y (1.24), N (0.73), H (0.56), Mg (0.52), Ti (0.34), Si (0.34), C (0.33), Al (0.32), Ni (0.26), Ta (0.23), and Mn (0.16). The presence of these elements in Fe matrix could reduce the transport of He towards oxide particles, dislocations, and internal boundaries, and could promote He bubble nucleation in the matrix. For convenience, we compile existing binding energy data of He with He n and He n V (He-vacancy) clusters. Dissociation pathway analysis reveals that, in general, the most likely dissociation of a He n V cluster is by a sequential emission of individual He atoms. Furthermore, larger bubbles are more prone to dissociation than smaller ones. In addition, we estimate the binding energy (segregation energy) of He in bulk Y 2 Ti 2 O 7 (YTO) single crystal, YTO/Fe interface, and YTO particle embedded in Fe, with respect to interstitial He in Fe, from existing formation energies of He in these structures. We also compile available data of He binding with Fe self-interstitial atom (SIA), SIA clusters, and edge and screw dislocations. Note that given the absence of DFT data, the binding with SIA clusters and dislocations are gathered from simulations with empirical potentials. Finally, the data presented in this paper is important to inform multiscale simulations of He bubble accumulation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Semiclassical model for calculating exciton and polaron pair energetics at interfaces

Exciton and polaron pair dissociation is a key functional aspect of photovoltaic devices. To improve upon the current state of interfacial transport models, we augment the existing classical models of dielectric interfaces by incorporating results from ab initio calculations, allowing us to calculate exciton and polaron binding energies more accurately. We demonstrate the predictive capabilities of this new model using two interfaces: (i) the boron subphthalocyanine chloride (SubPc) and C60 interface, which is an archetype for many organic photovoltaic devices; and (ii) pentacene and silicon (1 0 0), which represents a hybrid between organic and inorganic semiconductors. Overall, our calculations predict that the insertion of molecular dipoles at interfaces can be used for improving polaron pair dissociation and that sharp transitions in dielectric permittivity can have a stronger effect on the polaron pair dissociation than even the electron-hole Coulomb interaction.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Sensitivity study of hydrogen Soret transport in yttrium Hydride-Based nuclear fuel

Yttrium hydride is an excellent solid neutron moderator material for high temperature nuclear reactor applications due to its high hydrogen density and exceptional hydride stability at high temperatures. Despite these attractive characteristics, the details of how hydrogen behaves within yttrium hydride while temperature gradients exist are still not well understood. The evolution of the hydrogen composition profile resulting from a temperature gradient requires knowledge of hydrogen’s heat of transport, a critical parameter that has not yet been measured for this material. In this work, we perform hydride redistribution, hydrogen dissociation, and hydrogen leakage calculations while varying the Soret heat of transport of hydrogen in yttrium hydride to elucidate the sensitivity of hydride stability under temperature gradients to this parameter. This study analyzes hydride stability of a hypothetical uranium-yttrium hydride nuclear fuel design during operation of a high temperature liquid metal-cooled nuclear reactor. Assuming U-YH x could be fabricated in a physically stabilized manner, this fuel system can likely maintain hydride stability while operating at very high power densities and temperatures. We find that even though the hydrogen dissociation pressure in the gas gap does vary by several percent as the heat of transport temperature parameter is varied, the hydrogen content in the U-YH x fuel meat is relatively insensitive to this parameter over the course of a high burnup fuel cycle; this is due to yttrium hydride’s excellent hydrogen retention under the high temperature conditions considered here. Here, this suggests that hydride stability analyses are insensitive to the value of the Soret heat of transport in U-YH x under steady state liquid metal-cooled reactor conditions. However, the susceptibility to internal gas overpressurization-induced stress-rupture of the cladding during a high temperature transient is more sensitive to this parameter due to the non-linear dependence of hydrogen gas dissociation pressure vs. composition and temperature.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Kinetics of low temperature plasma assisted NH 3 /H 2 oxidation in a nanosecond-pulsed discharge

Ammonia (NH 3 ) has been widely recognized as one of the carbon-neutral fuels. However, ammonia combustion suffers low reactivity and high N 2 O/NO x emissions. Here, to overcome these issues, this work reports plasma assisted NH 3 /H 2 oxidation and unveils the kinetics of fuel oxidation and N 2 O/NO x formation by combining time-resolved laser diagnostics with plasma modeling. Firstly, we found that the NH 3 consumption is promoted with a H 2 blending ratio of 0.3, due to enhancements of H and OH formation by plasma assisted H 2 dissociation. Secondly, at a high reduced electric field, when the H 2 blending ratio increases, the NH 3 oxidation is promoted due to both the HO 2 formation and strong NO kinetic enhancement via NO-HO 2 and NO 2 -H pathways. In the meantime, it is shown that the NO mole fraction also increases with H 2 blending ratio, because the NO formation is enhanced via N( 2 D)-O 2 pathways, and the DeNO x chemistry is weakened with less NH 2 production. By contrast, at a lower reduced electric field, when the H 2 blending ratio increases, the decreased N( 2 D) formation does not produce enough NO to replenish the NO formation drop caused by lower NH 3 concentration. Thirdly, the reduced electric field non-monotonically affects fuel consumption and N 2 O/NO x formation by manipulating electron energy deposition pathways. The NH 3 consumption is maximized with an optimal reduced electric field where N 2 * excitation and O 2 dissociation are most efficient. When the reduced electric field deviates from its optimum, the NH 3 consumption decreases due to the discharge energy deposition to either vibrational excitation or dissociation of N 2 . The N 2 O/NO x emissions governed by the NH 3 oxidation follow the above NH 3 consumption trend.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Resolving Discrepancies Between Theory and Experiment for the NCN + H Reaction

Flame modeling studies have highlighted the role of branching in the kinetics for the prompt NO switch reaction, NCN + H. In this reaction, there is strong competition between the CH + N2 (R1) and HCN + N (R2) product channels. Increased branching towards reaction R2 promotes the subsequent formation of Fenimore or Prompt NO. Recent direct shock tube studies on this complex reaction conclude that branching to reaction R2 is much more favorable than the predicted branching from theoretical studies. The experimentally predicted prompt NO switch temperature (TS), i.e., the temperature at which k2/(k1+k2) = 0.5, is at 1670 K, in contrast to theory that predicts Ts > 3200 K. The present theory/modeling work was initiated to highlight potential causes for this significant discrepancy between experiment and theory. Our analysis of the simulations reported in the experimental studies indicate that including a fall-off representation for C2H5 radical dissociation (with C2H5 produced from C2H5I dissociation and acting as an H-atom source) has a noticeable influence on the simulations for NCN decay and HCN formation in the shock tube studies. With the inclusion of a theory-based pressure fall-off representation for C2H5 dissociation, we show that this radical persists for much longer timescales even at the high-temperatures in the shock tube studies. This persistence then facilitates the rapid conversion of reactive H-atoms to CH3 radicals at the shock tube conditions via the H + C2H5 → CH3 + CH3 reaction. An updated theoretical analysis for this classic addition-elimination reaction is also provided in this work. The rapid formation of CH3 radicals necessitates the inclusion of additional reactions to adequately simulate the NCN and HCN data. Our simulations conclude that, with the inclusion of these additional reactions, the NCN and HCN profiles can be reasonably well simulated by the most recent theoretical predictions.

Ethyl Radicals↗
DOE OSTI2021

Defining optimal enzyme and matrix combination for replating of human induced pluripotent stem cell-derived cardiomyocytes at different levels of maturity

Human induced pluripotent stem cell-derived cardiomyocytes (hiPSC-CM) create an unlimited cell source for basic and translational research. Depending on the maturity of cardiac cultures and the intended applications, obtaining hiPSC-CMs as a single-cell, monolayer or three-dimensional clusters can be challenging. Here, we defined strategies to replate hiPSC-CMs on early days (D15-30) or later more mature (D60-150) differentiation cultures. After generation of hiPSCs and derivation of cardiomyocytes, four dissociation reagents Collagenase A/B, Collagenase II, TrypLE, EDTA and five different extracellular matrix materials Laminin, iMatrix-511, Fibronectin, Matrigel, and Geltrex were comparatively evaluated by imaging, cell viability, and contraction analysis. For early cardiac differentiation cultures mimicking mostly the embryonic stage, the highest adhesion, cell viability, and beating frequencies were achieved by treatment with the TrypLE enzyme. Video-based contraction analysis demonstrated higher beating rates after replating compared to before treatment. For later differentiation days of more mature cardiac cultures, dissociation with EDTA and replating cells on Geltrex or Laminin-derivatives yielded better recovery. Cardiac clusters at various sizes were detected in several groups treated with collagenases. Collectively, our findings revealed the selection criteria of the dissociation approach and coating matrix for replating iPSC-CMs based on the maturity and the requirements of further downstream applications.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Bipolar Membranes for Ion Management in (Photo)Electrochemical Energy Conversion

Conspectus (Photo)electrochemical energy conversion is important in the development of a carbon-neutral energy economy because it can provide a pathway for mitigating the intermittency of renewable energy sources such as wind and solar. In order to operate efficiently, these technologies, which include photoelectrochemical cells, water and CO 2 electrolyzers, fuel cells, and redox flow batteries, require fast charge transfer kinetics at the electrode/electrolyte interface as well as robust ion management in the electrolyte. In conventional electrolyzers and fuel cells, the electrolyte is strongly acidic or basic and ionic current is carried by H + or OH – ions. In contrast, photoelectrodes and electrocatalysts for water splitting are often studied in buffered solutions. The question of ion balance in these systems led us to analyze the polarization losses due to ion concentration gradients in cells that employed various buffer–membrane combinations. Continuously driving the buffer ions across an ionomer membrane not only lowers the buffer capacity of an aqueous electrolyte but also introduces pH gradients that result in significant energy losses. To address the problem, we and other groups have studied the use of reverse-biased bipolar membranes (BPMs) in (photo)electrolytic cells. BPMs consist of an anion exchange layer (AEL) laminated with a cation exchange layer (CEL) and are usually equipped with a catalytic layer in between to accelerate the water dissociation reaction. At the AEL/CEL interface, water dissociates into protons and hydroxide ions, which replenish those consumed at the cathode and anode. Compared to conventional water electrolyzers with proton/anion exchange membranes (PEM/AEM), BPM electrolyzers provide the unique advantage of continuously operating the cathode and anode under different pH conditions, which is desirable when the two electrode reactions have different pH requirements. BPMs also enable the use of buffered electrolytes at pH values that are optimized for electrode stability and product selectivity in applications such as CO 2 electrolysis. Product crossover losses and CO 2 pumping can be dramatically reduced in BPM-based CO 2 electrolyzers, relative to conventional alkaline membranes, by electrostatic repulsion (of anionic products) and electroosmotic drag (for neutral products). BPM-based gas fed CO 2 electrolyzers can achieve high current density, but they suffer from low Faradaic efficiency (FE) due to the acidic local environment of the CEL. This problem can be mitigated by adding an aqueous buffering layer or by creating a weak acid cation exchange film on the CEL face of the membrane. The use of BPMs in fuel cells and redox flow batteries offers some interesting advantages. Configurations with both reverse and forward bias have been studied, but forward bias has been favored due to material compatibility, reaction kinetics, and thermodynamic considerations. The net reaction at the AEL/CEL interface is the acid–base neutralization reaction, which has a high inherent reaction rate constant, but in the BPM is limited to a nanometric space-charge layer and requires efficient catalysis to achieve high current density. Understanding the mechanism of the acid–base neutralization and the opposite process, the water dissociation reaction, will be essential for improving the performance of forward-biased BPMs. In conclusion, this Account reviews our current understanding of the working mechanisms of BPMs and discusses how we can use them to effectively manage ions for various (photo)electrochemical applications.

Yan, Zhifei↗