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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 289 records · Page 16

Modulating thermal load through lightweight residential building walls using thermal energy storage and controlled precooling strategy

Precooling is a recognized technique for reducing cooling energy in buildings during peak hours by shifting load to off-peak hours. This technique is particularly effective in buildings with high thermal mass, because of their large thermal energy storage capacity, and in commercial buildings due to their variable electricity pricing based on time-of-use rates. Precooling in residential buildings has been a matter of limited interest in the past because of their low thermal mass and typically uniform electricity pricing rate. While previous studies on precooling primarily focused on cost savings, an important aspect of precooling is the thermal load modulation, which could be very effective in managing peak demand in lightweight residential buildings integrated with thermal energy storage systems. In this study, we examine different precooling strategies to manage the heat gains in lightweight building walls integrated with phase-change materials. We create nine different precooling profiles by controlling the interior temperature, and then evaluate the influence of the precooling profiles on four key building energy performance parameters: total heat gain, peak heat gain, maximum heat gain during peak hours, and time at which peak occurs. To thoroughly understand the fundamental physics, we first consider hypothetical climates and obtain the optimal precooling strategy required to achieve maximum peak shedding and shifting while minimizing the total heat gains. We then extend the model to Baltimore, Maryland, and estimate the benefits of the optimized precooling strategy under real conditions. The optimal precooling strategy proposed in this study can shift the peak heat gain by up to 14 hours, thereby reducing the heat gain during peak period by up to 95%, at the expense of a 23% increase in the total heat gains.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Gas transport characteristics of supramolecular networks of metal-coordinated highly branched Poly(ethylene oxide)

Model systems are developed and investigated to better understand the effect of polyether-metal ion interactions on gas separation characteristics. These systems help answer current questions raised by the substantial body of research on metal-organic frameworks (MOFs) dispersed in polyethers to improve gas separation performance, where favorable interactions between the metal centers and polyethers are preferred to improve interfacial compatibility. Specifically, we investigate CO 2 /gas transport properties of supramolecular networks comprising cross-linked poly(ethylene oxide) (XLPEO) and dissociable salts, including LiClO 4 , Ni(BF 4 ) 2 , and Cu(BF 4 ) 2 . Increasing the salt content increases the glass transition temperature (T g ) and generally decreases gas diffusivity and permeability, which can be successfully described using a T g -integrated free volume model with an expression similar to the Vogel-Tammann-Fulcher (VTF) equation. Surprisingly, low loadings of LiClO 4 and Cu(BF 4 ) 2 (2 mass% or less) can increase gas permeability by 30%–70% without affecting the CO 2 /gas selectivity. This increase correlates with polyether-metal ion dynamics as measured by dielectric spectroscopy. Understanding how interaction-mediated dynamics affect gas transport will be instrumental to designing MOF-based mixed matrix materials for gas separations.

36 MATERIALS SCIENCE↗

A Novel Multiagent Resource Sharing Algorithm for Control of Advanced Energy Systems

This paper implements a novel resource sharing control strategy on a fuel cell–gas turbine hybrid power system at the National Energy Technology Laboratory’s Hybrid Performance Facility (Hyper). In a fuel cell–gas turbine hybrid power system, the simultaneous interaction of the gas turbine and the fuel cell creates a tightly coupled environment characterized by conflicting dynamics. In this paper, a model-free control approach is applied to solve the tightly coupled control problem posed by this challenging environment. Specifically, this control problem is presented as a resource sharing problem that can be solved using a resource sharing algorithm that is defined based on the distribution construction concept. This algorithm creates computational agents and solves the problem through the distribution and redistribution of shared resources defined as blocks. Furthermore, two agents were created; the first agent (agent 1) controls the gas turbine speed by adjusting the electric load, and the second agent (agent 2) controls the cathode mass flow through the fuel cell using the cold-air bypass valve. A parametric study was performed over the course of 15 experimental tests for both agents 1 and 2 through an evaluation of the responses based on setpoint changes. The algorithm was shown to have behavior comparable to a previously implemented multi-input multioutput state-space controller, which was designed through a model-based control approach. The resource sharing algorithm was able to find stable performance during run-time operations without any prior system knowledge identification on the power plant and without creating models used in traditional control strategies.

25 ENERGY STORAGE↗

Investigating the Role of Polymer Architecture in Poly(methyl methacrylate) Depolymerization

Advanced architectures in polymers have garnered traction within the last two decades due to their distinct and tunable properties compared to linear analogs. However, the effects of architecture on nascent polymethacrylate depolymerization strategies remain underexplored. Herein, we investigate the depolymerization behavior of poly(methacrylate)-based star copolymers synthesized via a core-first approach. By incorporating either labile chain-end or pendent-group triggers, we demonstrate the first direct comparison of bulk depolymerization behaviors in star versus linear methacrylate copolymers under matched conditions. While pendent-triggered systems required higher loadings of N-(methacryloxy)phthalimide methacrylate (PhthMA) to achieve similar mass loss compared to linear copolymers, chain-end-initiated depolymerization showed enhanced efficiency of monomer liberation in the star topology. Furthermore, these findings highlight the importance of considering macromolecular architecture in designing sustainable polymers and provide actionable guidelines for installing depolymerization triggers based on polymer topology.

Copolymers↗

Adaptively controlled fast production of defect-free beryllium ion crystals using pulsed laser ablation

Trapped atomic ions find wide applications ranging from precision measurement to quantum information science and quantum computing. Beryllium ions are widely used due to the light mass and convenient atomic structure of beryllium; however, conventional ion loading from thermal ovens exerts undesirable gas loads for a prolonged duration. Here, we demonstrate a method to rapidly produce pure linear chains of beryllium ions with pulsed laser ablation, serving as a starting point for large-scale quantum information processing. Our method is fast compared to thermal ovens, reduces the gas load to only 10 -12 Torr (10 -10 Pa) level, yields a short recovery time of a few seconds, and also eliminates the need for a deep ultraviolet laser for photoionization. We also study the loading dynamics, which show non-Poissonian statistics in the presence of sympathetic cooling. In addition, we apply feedback control to obtain defect-free ion chains with desirable lengths.

47 OTHER INSTRUMENTATION↗

Flattop-HEU Benchmark Reevaluation Summary

The Flattop critical assembly was first constructed in the 1950’s at Los Alamos National Laboratory as a follow-on to the Topsy experiment. Flattop is composed of a sphere of special nuclear material (SNM) surrounded by a thick spherical reflector made of natural uranium (NU). Two SNM cores currently exist: a highly-enriched-uranium (HEU) core and a plutonium core. The reflector is composed of three parts: a stationary hemisphere and two movable quarter spheres. For fine reactivity control, there are three control rods of NU that are inserted into the stationary hemisphere from underneath the assembly. The final components that allow for reactivity adjustment are the glory hole pieces, mass adjustment buttons, and hemispherical caps. These pieces can be loaded in various configurations to change the available reactivity loaded in the system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Summary of Expedited Results from Samples Supporting Tank Closure Cesium Removal (TCCR) Batch 3

Savannah River Remediation (SRR) is currently operating the Tank Closure Cesium Removal (TCCR) process to remove 137 Cs from tank waste supernate using an ion exchange process. As part of that process, Savannah River National Laboratory (SRNL) receives and analyzes samples in support of the qualification of each batch to be processed. SRNL recently received supernate samples retrieved from Tank 10H as well as in-tank batch contact samples for characterization in support of qualifying Batch 3 for processing through the TCCR unit. SRNL received and characterized a set of dip samples collected from Tank 10H (one surface and one variable depth sample). No solids were observed in either sample and therefore the samples were combined, and a suite of analyses were performed on the composite sample. The density of the combined sample was 1.174 g/mL (0.18 %RSD), which was consistent with the measured sodium concentration of 3.54 M (0.08 %RSD). The 137Cs activity in the sample was 4.75E+07 dpm/mL (4.28 %RSD) and the total Cs concentration was calculated to be 1.54 mg/L (1.16E-05 M). The in-tank batch contact samples consist of 0.1 g of crystalline silicotitanate (CST) contained within a teabag device. Duplicate samples were submerged in Tank 10H supernate for a period of about 13 days, after which time they were retrieved and transferred to SRNL for analysis. At SRNL the CST was rinsed to remove excess salt solution and the CST was then air dried before being digested for analysis. Results of the analysis indicated a 137 Cs loading of 3.66E+10 ± 1.40E+09 dpm/g or 16.5 ± 0.63 Ci/kg CST . This value represents a bounding upper limit as it includes the addition of two sigma uncertainty from replicate analysis of the individual teabag samples as well as the addition of the small amount of 137 Cs activity measured in the rinse solutions. The above values are based on the air-dried mass of CST. Correcting to the true dry mass using a F-factor of 0.8191 results in a maximum loading of 20.2 ± 0.77 Ci/kg CST .

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

SPE-CZE-MS Quantifies Zeptomole Amounts of Phosphorylated Peptides

Capillary zone electrophoresis (CZE) is gaining attention in the field of single-cell proteomics for its ultralow-flow and high-resolution separation abilities. Even more sample-limited yet rich in biological information are phosphoproteomics experiments, as the phosphoproteome composes only a fraction of the whole cellular proteome. Rapid analysis, high sensitivity, and maximization of sample utilization are paramount for single-cell analysis. Some challenges of coupling CZE analysis with mass spectrometry analysis (MS) of complex mixtures include 1. sensitivity due to volume loading limitations of CZE and 2. incompatibility of MS duty cycles with electropherographic time scales. Here, we address these two challenges as applied to singlecell- equivalent phosphoproteomics experiments by interfacing a microchip-based CZE device integrated with a solid-phaseextraction (SPE) bed with the Orbitrap Astral mass spectrometer. Using 225 phosphorylated peptide standards and phosphorylated peptide-enriched mouse brain tissue, we investigate microchip-based SPE-CZE functionality, quantitative performance, and complementarity to nano-LC-MS (nLC-MS) analysis. We highlight unique SPE-CZE separation mechanisms that can empower fitfor- purpose applications in single-cell-equivalent phosphoproteomics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Small to Full Height Scale Comparisons of Cesium Ion Exchange Performance with Crystalline Silicotitanate

The U.S. Department of Energy’s (DOE) Hanford Site houses 56 million gallons of high-level radioactive waste generated from plutonium production from 1944 to 1988. The supernatant waste, currently stored in underground tanks, is intended to be vitrified following filtration and 137 Cs removal at the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Vitrification Facility. The WTP Pretreatment Facility will not be operational for several years. The Tank Side Cesium Removal (TSCR) system is a technology demonstration that will remove cesium from tank waste supernate to support directly feeding LAW to the vitrification facility. The 137 Cs removal is important to meet the WTP LAW contract specification and ultimately for creating a contact-handled waste form. The waste acceptance criteria (WAC) limit for the WTP LAW Facility is <3.18E-5 Ci 137 Cs per mole Na. The TSCR system is skid mounted and employs two key technologies: dead end filtration for solids removal and ion exchange (IX) for cesium removal. Filtration is necessary to protect the functionality of the IX columns. The IX process utilizes sodium form crystalline silicotitanate (CST) IX media produced by UOP Honeywell, LLC (Des Plaines, IL) under the product name IONSIV R9140-B, 18 x 50 mesh, in a lead-lag-polish column configuration. Each column contains a CST bed height of 92 inches and a volume of approximately 157 gallons of CST IX media. The full-scale TSCR operation will run at a residence time of 1.9 bed volumes (BV)/h, which results in a superficial velocity of 7.3 cm/min and a flowrate of ~5 gal/min. Column testing at small (2.5% of the full bed height), medium (12% of the full bed height), and full-height scales has been previously conducted to evaluate process variables and scale up performance of Cs exchange onto the CST. Cesium load performances from various sieve cuts at the small scale indicated that a 30-mesh sieve cut be tested to determine if it better reflects the 12% and full-height column performances at the small scale. Two process flowrates were tested in the small-column configuration with <30-mesh CST and simulant solutions. These tests were compared to full-height column tests at the same residence times to assess CST particle size effect on column scaling. Table S.1 summarizes the observed column performance determined for the two flowrates juxtaposed to the previous work with 5.6 M Na simulant at higher scales (used as benchmarks). The WAC breakthroughs between the small and full-height tests at 1.3 BV/h differed by ~59 BVs. The WAC breakthroughs for small, medium, and full-height tests at 1.8 BV/h were consistent at 240 BVs. The 50% Cs breakthroughs were nominally equivalent for all column tests. The common transition zones and onsets of Cs breakthrough at the 1.8 BV/h tests indicated that the Cs mass transfers were equivalent and thus the <30-mesh CST Cs load performance at the small scale successfully modeled that of the full-height system. It is recommended that the <30-mesh CST be used in subsequent 10-mL CST bed tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

EWTN: Quantifying Mass Transport to Enable Water Electrolyzer Architectures with Low Flow-Rate Sensitivity

To develop cost-effective and high-performing polymer electrolyte water electrolyzers (PEWEs) for gigawatt-scale applications, researchers have focused on reducing precious metal catalyst loadings and optimizing porous transport layers. However, the performance of PEWEs is also affected by system architecture. Mass transport losses are dependent on localized architecture and material interactions. In-situ measurements, such as current density distribution maps have demonstrated advantages in understanding the intricate characteristics and influence of two-phase flow within PEWEs. This study proposes the parameter of effective water transport number (EWTN) as a quantitative tool to investigate such current density distribution (CDD) measurements for PEWEs. Results show that higher flow-rates have EWTN values of 0.95 and above, indicating no mass transport limitations; while lower flow-rates with large gradients CDD have EWTN values between 0.6-0.8, indicating mass transport limited conditions. The new analysis also identified a correlation between mass transport losses due to bubble accumulation, membrane hydration, and ohmic overpotentials. To address these limitations, an unitized pin-type LGDL/flow-field design was developed, which effectively prevents local gas phase accumulation, resulting in improved mass transport characteristics. The results of this work show reduced flow-rate sensitivity with the pin-type architecture and ∼13% increased performance at 0.24 ml / min / cm 2 .

Electrochemistry↗

Large-scale simulation-based parametric analysis of an optimal precooling strategy for demand flexibility in a commercial office building

Achieving success with grid-interactive efficient buildings (GEBs) is closely tied to the utilization of flexible loads. A valuable strategy involves the implementation of precooling techniques before high-demand events, such as peak hours, by adjusting zone air temperature setpoints. This leads to a reduction in thermal loads and peak electricity demand during these times, as the building’s thermal mass stores and subsequently releases thermal energy. However, the effectiveness of the pre-cooling optimization is highly contingent on specific conditions such as building thermal properties, weather conditions, utility rate structure, HVAC equipment sizing, etc. Therefore, investigating the impacts of these condition-specific factors is crucial, especially when considering precooling strategies that utilize thermal mass in commercial buildings. In this paper, we first devised a novel heuristic control approach that incorporates parameterized optimal precooling thermostat schedules to enhance demand flexibility in a commercial office building. Subsequently, we conducted a thorough performance evaluation of this control strategy. Here, the optimal thermostat schedule was parameterized using three optimization variables: the precooling start time, the precooling end time, and the precooling temperature setpoint. Utilizing the DOE medium-sized office building as the virtual testbed, we showed that the parameterized schedule effectively approximates model predictive control and requires drastically reduced computational overhead. In addition, we investigated the impact of different influencing factors on the optimal precooling strategy. These factors include building thermal mass, outdoor air conditions, and energy price profiles. Using high-performance computing, we simulated a total of 225 scenarios, consisting of three levels of thermal mass, five typical outdoor air temperature profiles, and fifteen time-of-use price plans. The results demonstrate that optimal thermostat scheduling could save substantial energy cost in medium-sized office buildings with heavy thermal mass but with some energy penalty. Although the potential for cost savings is lower in buildings with low and medium thermal mass, the energy penalty remains consistent in all three thermal mass scenarios. The study also highlights the need to account for zone diversity and recognize that a one-size-fits-all-zone setpoint schedule may not be suitable for all zones and can lead to unnecessary energy wastage. Furthermore, the results highlight that while outdoor air conditions play a role in cost and energy performance, the cooling load exerts a more immediate and substantial influence on cost savings in precooling strategies. Although cost savings are comparable under certain conditions with the same cooling load, observed deviations in energy penalty indicate potential disparities in the efficiency of the HVAC system during the load-shifting process. In addition, the duration of peak pricing and the ratio between peak and off-peak times exhibit clear correlations with cost savings and energy consumption, aligning with intuitive expectations. These findings offer valuable insights for optimizing precooling strategies in office buildings.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Design of a 3.4-MW wind turbine with integrated plasma actuator-based load control

Historically, cost reduction in wind energy has been accomplished by increasing hub heights and rotor diameters to capture more energy per turbine. The growth in rotor and turbine costs with increasing turbine sizes is also driven by the additional structure that must be added to withstand unsteady aerodynamic loads caused by turbulence, gusts, wind shear, misaligned yaw, upwind wakes, and the tower shadow. In this paper, we present a holistic design solution to integrate active load control using a controllable Gurney flap based on plasma actuators. We illustrate the design solution for a land-based 3.4-MW wind turbine rotor. Comparisons to a baseline reference 3.4-MW wind turbine show significant load reduction (15–18% DEL reduction for flap-wise blade root moments), rotor mass reduction (5–8%), and LCOE reduction (1.16–3.11%). To achieve these results, a comprehensive sequential-iterative design procedure is introduced to integrate the controllable Gurney flap into the turbine design and to drive the design solution toward the best LCOE reduction solution. Results are presented for mapping fatigue load reductions into cost reductions. In addition, an evaluation of active load control extended from Region-III to also include Region-II showed a further 34% reduction in DEL.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Evaluation of Getter Metals in Na–Al–Si–O Aerogels and Xerogels for the Capture of Iodine Gas

In this paper, sodium aluminosilicate aerogels and xerogels were evaluated as scaffolds for a variety of different getters including: Ag + , Cs + , Cu 2+ , Fe 3+ , K + , Li + , Rb + , Sb 3+ , Sn 2+ , and Sn 4+ . The exchange capacities varied widely from a near complete exchange in the case of Ag + to much lower exchange levels for some of the Sn compounds [i.e., colloidal SnO 2 , Sn(II) acetate, Sn(IV) acetate]. Several of the additives showed great promise at allowing for high iodine loadings in the base materials including the following: AgNO 3 , colloidal SnO 2 , Sn(II) acetate, Sn(IV) acetate, Cu(NO 3 ) 2 , and CuSO 4 . From the standpoint of iodine uptake as a function of getter loading, the Sn4+ showed the most promise with a getter utilization (mass of iodine divided by mass of Sn, in atomic%) of 8.4, a chemical uptake of 60.7 mass% (oxygen excluded), and an mI $m_s^{-1}$ value of 0.881; these are some of the highest values reported to date for inorganic iodine sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discrimination between individual dust and bioparticles using aerosol time-of-flight mass spectrometry

Ice nucleating particles (INPs) impact cloud properties and precipitation processes through their ability to trigger cloud glaciation. Dust and bioparticles are two important sources of INPs that have markedly different atmospheric loadings and ice nucleating efficiencies. In situ identification of the sources of INPs in clouds has been accomplished using single particle mass spectrometry (SPMS). However, external mixtures of dust and bioparticles present a unique challenge as they have overlapping mass spectral ion signatures, complicating their unambiguous identification. This study presents a detailed discussion of dust and bioparticle SPMS signatures, uniting data from a broad array of studies. As emphasized, the ion signals from both dust and bioparticles are highly sensitive to ionization conditions. To understand the observed variations, we characterize the mass spectral dependence of distinct dust and bioparticle samples using total positive ion intensity (TPII) as an indicator of the laser pulse energy each particle encountered. Through this analysis, a broad range of characteristic biogenic low intensity ion peaks that may be useful to distinguish bioparticles from dust became apparent and are highlighted. Insights informed by this analysis were utilized to identify bioparticles in ambient SPMS data. Ambient particles exhibiting both dust and characteristic biogenic spectral fingerprints were excluded from the bioparticle classification. Although bioparticles only made up 0.2% of all sampled particles, their abundance was moderately correlated with INP concentrations measured at 15 °C.

54 ENVIRONMENTAL SCIENCES↗

Investigation of Theoretical Solutions to a Bottom-Raised Oscillating Surge Wave Energy Converter (OSWEC) Through Experimental and Parametric Studies

Experiments were conducted on a wave tank model of a bottom raised oscillating surge wave energy converter (OSWEC) model in regular waves. The OSWEC model shape was a thin rectangular flap, which was allowed to pitch in response to incident waves about a hinge located at the intersection of the flap and the top of the supporting foundation. Torsion springs were added to the hinge in order to position the pitch natural frequency at the center of the wave frequency range of the wave maker. The flap motion as well as the loads at the base of the foundation were measured. The OSWEC was modeled analytically using elliptic functions in order to obtain closed form expressions for added mass and radiation damping coefficients, along with the excitation force and torque. These formulations were derived and reported in a previous publication by the authors. While analytical predictions of the foundation loads agree very well with experiments, large discrepancies are seen in the pitch response close to resonance. These differences are analyzed by conducting a sensitivity study, in which system parameters, including damping and added mass values, are varied. The likely contributors to the differences between predictions and experiments are attributed to tank reflections, standing waves that can occur in long, narrow wave tanks, as well as the thin plate assumption employed in the analytical approach.

analytical↗

Label-Free Profiling of up to 200 Single-Cell Proteomes per Day Using a Dual-Column Nanoflow Liquid Chromatography Platform

Single-cell proteomics (SCP) has great potential to advance biomedical research and personalized medicine. The sensitivity of such measurements increases with low-flow separations (<100 nL/min) due to improved ionization efficiency, but the time required for sample loading, column washing, and regeneration in these systems can lead to low measurement throughput and inefficient utilization of the mass spectrometer. Herein, we developed a two-column liquid chromatography (LC) system that dramatically increases the throughput of label-free SCP using two parallel subsystems to multiplex sample loading, online desalting, analysis, and column regeneration. The integration of MS1-based feature matching increased proteome coverage when short LC gradients were used. The high-throughput LC system was reproducible between the columns, with a 4% difference in median peptide abundance and a median CV of 18% across 100 replicate analyses of a single-cell-sized peptide standard. An average of 621, 774, 952, and 1622 protein groups were identified with total analysis times of 7, 10, 15, and 30 min, corresponding to a measurement throughput of 206, 144, 96, and 48 samples per day, respectively. When applied to single HeLa cells, we identified nearly 1000 protein groups per cell using 30 min cycles and 660 protein groups per cell for 15 min cycles. Finally, we explored the possibility of measuring cancer therapeutic targets with a pilot study comparing the K562 and Jurkat leukemia cell lines. This work demonstrates the feasibility of high-throughput label-free single-cell proteomics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pushing Lithium–Sulfur Batteries towards Practical Working Conditions through a Cathode–Electrolyte Synergy

Abstract The commercialization of lithium–sulfur (Li−S) batteries is still hindered by the unsatisfactory cell performance under practical working conditions, which is mainly caused by the sluggish cathode redox kinetics, severe polysulfide shuttling, and poor Li stripping/plating reversibility. Herein, we report an effective strategy by combining Se‐doped S hosted in an ordered macroporous framework with a highly fluorinated ether (HFE)‐based electrolyte to simultaneously address the aforementioned issues in both cathode and anode. A reversible and stable high areal capacity of >5.4 mAh cm −2 with high Coulombic efficiency >99.2 % can be achieved under high areal Se/S loading (5.8 mg cm −2 ), while the underlying mechanism was further revealed through synchrotron X‐ray probes and Time‐of‐Flight Secondary Ion Mass Spectrometry (ToF‐SIMS). The practical application potential was further evaluated at low (0 °C) and high (55 °C) temperatures under high areal Se/S loading (>5.0 mg cm −2 ) and thin Li metal (40 μm).

Zhao, Chen↗

Electrolysis on a Chip with Tunable Thin Film Nanostructured PGM Electrocatalysts Generated from Self-Assembled Block Copolymer Templates

Self-assembled block copolymers are promising templates for fabricating thin film materials with tuned periodic feature sizes and geometry at the nanoscale. Here, a series of nanostructured platinum and iridium oxide electrocatalysts templated from poly(styrene)-block-poly(vinyl pyridine) (PSbPVP) block copolymers via an incipient wetness impregnation (IWI) pathway is reported. Both nanowire and nanocylinder electrocatalysts of varying feature sizes are assessed and higher catalyst loadings are achieved by the alkylation of the pyridine moieties in the PVP block prior to IWI. Electrocatalyst evaluations featuring hydrogen pump and water electrolysis demonstrations are carried out on interdigitated electrode (IDE) chips flexible with liquid supporting electrolytes and thin film polymer electrolytes. Notably, the mass activities of the nanostructured electrocatalysts from alkylated block copolymer templates are 35%–94% higher than electrocatalysts from non-alkylated block copolymer templates. Standing cylinder nanostructures lead to higher mass activities than lamellar variants despite their not having the largest surface area per unit catalyst loading demonstrating that mesostructure architectures have a profound impact on reactivity. Overall, IDE chips with model thin film electrocatalysts prepared from self-assembled block copolymers offer a high-throughput experimental method for correlating electrocatalyst nanostructure and composition to electrochemical reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗