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At least 343 records · Page 19

Understanding Function and Performance of Carbon Additives in Lead-Acid Batteries

While the low cost and strong safety record of lead-acid batteries make them an appealing option compared to lithium-ion technologies for stationary storage, they can be rapidly degraded by the extended periods of high rate, partial state-of-charge operation required in such applications. Degradation occurs primarily through a process called hard sulfation, where large PbSO 4 crystals are formed on the negative battery plates, hindering charge acceptance and reducing battery capacity. Various researchers have found that the addition of some forms of excess carbon to the negative active mass in lead-acid batteries can mitigate hard sulfation, but the mechanism through which this is accomplished is unclear. In this work, the effect of carbon composition and morphology was explored by characterizing four discrete types of carbon additives, then evaluating their effect when added to the negative electrodes within a traditional valve-regulated lead-acid battery design. The cycle life for the carbon modified cells was significantly larger than an unmodified control, with cells containing a mixture of graphitic carbon and carbon black yielding the greatest improvement. The carbons also impacted other electrochemical aspects of the battery (e.g., float current, capacity, etc.) as well as physical characteristics of the negative active mass, such as the specific surface area.

25 ENERGY STORAGE↗

Performance of Microreactor Test Article with Embedded Sensors During Testing in The Single Primary Heat Extraction and Removal Emulator

The nuclear industry is pursuing microreactors that can be factory assembled and deployed to remote regions for reliable power generation. One class of microreactors uses a monolithic metal core block coupled to heat pipes that use passive heat flow, increasing the surface area for heat transfer without requiring active coolant flow through the reactor core. Additional experimental testing is required to understand the heat rejection limitations of heat pipes and thermal stresses in the monolithic core block due to significant temperature gradients. This report describes the initial characterization and testing of a stainless-steel test article that was fabricated with embedded sensors to measure heat pipe performance limits, as well as spatially distributed temperatures and strains during electrically heated thermal testing to simulate nuclear heating. The electrically heated testing was performed in the Single Primary Heat Extraction and Removal Emulator facility located at Idaho National Laboratory. The ultimate goals of this work are to (1) accurately monitor temperature and strain distributions that result from differential thermal expansion in the test articles and (2) quantify the heat rejection limits of heat pipes as a function of operating temperature and working fluid during steady-state and transient operations. Initial tests focused on the feasibility of using advanced fiber-optic sensors and other sensor technologies to improve the understanding of temperature and strain distributions within the electrically heated experiments. However, these sensing capabilities could benefit the broader microreactor community if the sensors could be used to monitor component and system health during nuclear operations to inform a limited number of microreactor operators, ultimately reducing operation and maintenance costs and moving toward semiautonomous operation.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Chemo-Mechanically Driven In Situ Hierarchical Structure Formation in Mixed Conductors (Final Technical Report)

This document is the Final Technical Report for the Early Career project DE-SC0018963. Essential materials for energy technologies tend to exhibit “hierarchical” functions – they perform multiple, inter-related tasks at different locations, across disparate length and time scales. To best support this heterogeneous function, there is a fundamental need to understand and direct formation of corresponding tailored hierarchical architectures. In particular, a wide variety of applications, from energy conversion and storage to sensing and gas separation, rely on oxide mixed ionic and electronic conductors (MIECs). These critical ceramic materials catalyze reactions at their surfaces and selectively transport both ionic and electronic species in the bulk. Ideally, MIECs should adopt hierarchical structures with 1) high surface areas, 2) surface compositions exhibiting high catalytic activity, and 3) microstructural connectivity in the direction needed for fast mass and charge transport. In practice, however, MIECs.

08 HYDROGEN↗

High Aspect Ratio OLEDs

Long-term reliability is especially challenging for organic light emitting diodes (OLEDs) used in solid-state lighting applications because OLED lifetime is inversely proportional to luminance, and most lighting applications demand high luminance. This project explored a new strategy to overcome this tradeoff by constructing OLEDs on a substrate with sub-mm, high aspect ratio surface texture. By creating more active OLED area per unit lighting panel area, the device current density required to generate a given panel luminance decreases. We validated this approach for both fluorescent and phosphorescent OLEDs, demonstrating good thickness uniformity on corrugated substrates with area enhancement factors up to 1.4x using a standard thermal evaporator. Relative to planar controls at the same panel current density, the high aspect ratio devices achieve a 2.7-fold increase in operating lifetime and up to a 40% increase in external light extraction efficiency. Experiments carried out on a pilot-line OLED manufacturing system demonstrated good coating uniformity, indicating that this approach has the potential to be implemented at scale and therefore offers a powerful pathway to improve the efficiency and lifetime of OLED lighting.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Tribological applications of surface analysis

For some years, surface analysis was used in fundamental studies of solid-solid contacts existing in tribological systems. Analysis was used to detect material transfer in sliding contacts. The effects of surface films on the adhesion of contacts was monitored. Finally electron spectroscopic analysis of interfaces has shed some light on the fundamental electronic nature of the interfacial bond. More recently, surface analysis was applied to many tribological engineering problems. In particular, identification of chemical films formed during the sliding contact of lubricated systems and study of the surface chemistry of lubricant additives were active areas of research. One or more of four properties of the analytical technique will be important in determining its utility. The four are: lateral resolution, specimen damage, depth resolution and the availability of chemical information. In each of the applications discussed here, the important factors are brought out.

Wheeler, D. R.↗

COSMIC monthly progress report

Activities of the Computer Software Management and Information Center (COSMIC) are summarized for the month of August, 1993. Tables showing the current inventory of programs available from COSMIC are presented and program processing and evaluation activities are discussed. Ten articles were prepared for publication in the NASA Tech Brief Journal. These articles (included in this report) describe the following software items: (1) MOM3D - A Method of Moments Code for Electromagnetic Scattering (UNIX Version); (2) EM-Animate - Computer Program for Displaying and Animating the Steady-State Time-Harmonic Electromagnetic Near Field and Surface-Current Solutions; (3) MOM3D - A Method of Moments Code for Electromagnetic Scattering (IBM PC Version); (4) M414 - MIL-STD-414 Variable Sampling Procedures Computer Program; (5) MEDOF - Minimum Euclidean Distance Optimal Filter; (6) CLIPS 6.0 - C Language Integrated Production System, Version 6.0 (Macintosh Version); (7) CLIPS 6.0 - C Language Integrated Production System, Version 6.0 (IBM PC Version); (8) CLIPS 6.0 - C Language Integrated Production System, Version 6.0 (UNIX Version); (9) CLIPS 6.0 - C Language Integrated Production System, Version 6.0 (DEC VAX VMS Version); and (10) TFSSRA - Thick Frequency Selective Surface with Rectangular Apertures. Activities in the areas of marketing, customer service, benefits identification, maintenance and support, and dissemination are also described along with a budget summary.

Source record↗

Kinetic Measurements in Heterogeneous Catalysis

This contribution is about the experimental determination of the rate of a heterogeneous catalytic reaction and the analysis of kinetic data. In this case, the reaction rate can be defined as the frequency at which the closed sequence of elementary steps transforming reactants into products is occurring. However, the rate of chemical reaction is not directly observed; rather, one records the rate of substance change. The rate of chemical reaction is calculated based on the rate of substance change and assumed stoichiometry of the reaction. In order to make this an intensive quantity (i.e., independent of the volume in which the reaction is performed, this frequency is divided by the latter or by a quantity proportional to the latter). As the focus of what follows is on heterogeneously catalyzed reactions this can be the catalyst mass, the catalyst surface area or the total number of active sites present in the reaction volume confined by the walls of a chemical reactor. For example, the rate may be reported as one of the following: Net rate of consumption/production of component i mol m-3 s-1 Net specific rate of consumption/production of component i mol kg-1 s-1 Rate of substance change (per unit volume of catalyst) mol m-3 s-1 Specific reaction rate (per unit mass of catalyst) mol kg-1 s-1 Net rate of consumption/production of component i mol m-2 s-1 The turnover frequency (TOF) is a characteristic originally introduced by Boudart [1] is expressed as TOF=R/G_tot , where R is the steady-state rate of reactant consumption or product generation and G_totis the total areal density of active sites [mol m-2]. The latter is typically taken from experimental chemisorption data obtained at low temperature. The advancement of a chemical reaction leads to changes in the amounts of reactants and products which, for a stoichiometric single reaction, are connected by the stoichiometric coefficients. In many cases, for the sake of simplicity, we will assume that the investigated reaction proceeds according to a single reaction pathway, so that the net production rate of a reaction component is directly proportional to the reaction rate and that the latter equals the net production rate of any of the involved components when divided by the appropriate stoichiometric coefficient. For complex stoichiometric reactions the net production rates of the involved components are linear combinations of the reaction rates. Different goals for kinetic measurements can be formulated: Catalyst testing, i.e., obtaining the kinetic dependences for the development and discrimination of efficient catalytic materials. Precise kinetic characterization of active materials via high-throughput screening is a part of such activity. Detailed kinetics, i.e., revealing the detailed mechanism of complex catalytic reaction via systematic kinetic studies, both steady-state and non-steady-state Industrial kinetics, i.e., obtaining data and relationships for describing and predicting the behaviour of catalytic reactors and processes at industrial scale Finally, mathematical modeling and analysis where kinetic measurements provide data for understanding complex kinetic phenomena, e.g., oscillations, non-linear self-organization, etc.

36 MATERIALS SCIENCE↗

Uranium Mill Tailings Radiation Control Act Title II DOE Due Diligence and Lessons Learned from a Previous Site Transfer - 20352

Title II of the Uranium Mill Tailings Radiation Control Act (UMTRCA) established that a government agency will provide perpetual care for closed uranium and thorium ore-processing sites that were operating under an NRC source material license in 1978 or were licensed thereafter. Commercial owners (licensees) operating under an NRC or agreement state specific license when UMTRCA was passed are responsible for conducting reclamation of any byproduct material remaining from uranium-ore processing operations in accordance with an NRC or agreement state approved reclamation plan. Reclamation includes both surface and groundwater remedies. Upon completion of reclamation and approval by NRC, the site is required to be transferred to either the host state or the DOE for long-term surveillance and maintenance. Since UMTRCA's enactment, six Title II sites have been transferred to DOE; an additional 24 Title II sites are anticipated to be transferred before 2050. DoE's role mandated under UMTRCA Title II as the long-term care custodian is to perform 'monitoring, maintenance, and emergency measures necessary to protect the public health and safety.' UMTRCA requires that the licensee pay a long-term surveillance charge 'sufficient to cover the annual costs of site surveillance.' However, at some sites such as the Bluewater, New Mexico, Disposal Site, this mandate has required additional effort and expense by DOE, beyond the originally anticipated and intended scope within UMTRCA, but within the authority of DOE under UMTRCA. In 1997, the Bluewater site became the second UMTRCA Title II site to be transferred to DOE. The site was the location of a uranium mill operated from 1953 until 1982. The specific licensee began site reclamation in 1991, and by 1995 all tailings and contaminated materials were encapsulated in two tailings disposal cells and other disposal areas. In addition to surface contamination, milling activities impacted groundwater in the two upper aquifers. In 1989, the specific licensee attempted active groundwater remediation; however, no significant reduction in contaminant concentrations was observed. As a result, the specific licensee applied to NRC for alternate concentration limits (ACLs) in 1990, which were approved in 1996 as being protective, after additional corrective actions were performed. Since transfer of the Bluewater site to DOE, unforeseen challenges have occurred, requiring additional actions. The first challenge is the occurrence of surface depressions located on the northern section of the main tailings disposal cell. The depressions were first observed during DoE's initial inspection in 1998; however, evidence of these can be observed on satellite images taken prior to transfer. Since being first observed, the depressions have continued to grow both in depth and areal extent. Due to the design of the main tailings disposal cell, the depressions impede storm water from being effectively shed off the 101- hectare (250-acre) top slope of the main tailings disposal cell. Instead, storm water accumulates in the depressions, forming a large ephemeral pond that has stored up to 16.3 x 10{sup 6} liters (4.3 million gallons) of stormwater. The ponding poses a potential risk to the integrity of the main tailings disposal cell in the case of a large storm event, with the potential to cause the pond to overtop and erode the cover material and underlying waste. DOE has taken a number of short-term actions to monitor, measure, and reduce the ponding and is currently working with the US Army Corps of Engineers to design and construct a repair. Additional challenges are associated with groundwater at the Bluewater site. Nine wells were present on the 1335-hectare (3300-acre) site upon transfer. Groundwater compliance was called into question after the State of New Mexico reduced its uranium groundwater standard from 5.0 to 0.03 milligrams per liter in 2004, and when an ACL for uranium was exceeded in a site monitoring well in 2010. Acquiring historical groundwater data and subsequent evaluations as well as additional DOE groundwater monitoring led to installing 10 new monitoring wells and performing additional site hydrogeology recharacterization. DOE continues to evaluate groundwater conditions at the site and works with the NRC to determine regulatory requirements and a path forward. As a result of lessons learned at the Bluewater site and other Title II sites, improved processes have been implemented at a programmatic level to increase due diligence before site transfer and prevent similar issues from occurring at other UMTRCA Title II sites under long-term management. DoE's due diligence process is documented in the Process for Transition of UMTRCA Title II Disposal Sites to DOE for Long-Term Surveillance and Maintenance and is designed to ensure that DOE has no technical or compliance concerns with regulatory decisions that might compromise protectiveness following site transfer to DOE. Implementation of the due diligence process has increased DoE's role prior to site transfer and has been effective in identifying potential issues. Actions by NRC and specific licensees, in response to enhanced due diligence efforts by DOE, are expected to minimize, if not totally prevent, the need for unanticipated actions by DOE pertaining to the surface and groundwater remedies after site transfer. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Making Activated Carbon by Wet Pressurized Pyrolysis

A wet pressurized pyrolysis (wet carbonization) process has been invented as a means of producing activated carbon from a wide variety of inedible biomass consisting principally of plant wastes. The principal intended use of this activated carbon is room-temperature adsorption of pollutant gases from cooled incinerator exhaust streams. Activated carbon is highly porous and has a large surface area. The surface area depends strongly on the raw material and the production process. Coconut shells and bituminous coal are the primary raw materials that, until now, were converted into activated carbon of commercially acceptable quality by use of traditional production processes that involve activation by use of steam or carbon dioxide. In the wet pressurized pyrolysis process, the plant material is subjected to high pressure and temperature in an aqueous medium in the absence of oxygen for a specified amount of time to break carbon-oxygen bonds in the organic material and modify the structure of the material to obtain large surface area. Plant materials that have been used in demonstrations of the process include inedible parts of wheat, rice, potato, soybean, and tomato plants. The raw plant material is ground and mixed with a specified proportion of water. The mixture is placed in a stirred autoclave, wherein it is pyrolized at a temperature between 450 and 590 F (approximately between 230 and 310 C) and a pressure between 1 and 1.4 kpsi (approximately between 7 and 10 MPa) for a time between 5 minutes and 1 hour. The solid fraction remaining after wet carbonization is dried, then activated at a temperature of 500 F (260 C) in nitrogen gas. The activated carbon thus produced is comparable to commercial activated carbon. It can be used to adsorb oxides of sulfur, oxides of nitrogen, and trace amounts of hydrocarbons, any or all of which can be present in flue gas. Alternatively, the dried solid fraction can be used, even without the activation treatment, to absorb oxides of nitrogen.

Fisher, John W.↗

Automation and robotics human performance

The scope of this report is limited to the following: (1) assessing the feasibility of the assumptions for crew productivity during the intra-vehicular activities and extra-vehicular activities; (2) estimating the appropriate level of automation and robotics to accomplish balanced man-machine, cost-effective operations in space; (3) identifying areas where conceptually different approaches to the use of people and machines can leverage the benefits of the scenarios; and (4) recommending modifications to scenarios or developing new scenarios that will improve the expected benefits. The FY89 special assessments are grouped into the five categories shown in the report. The high level system analyses for Automation & Robotics (A&R) and Human Performance (HP) were performed under the Case Studies Technology Assessment category, whereas the detailed analyses for the critical systems and high leverage development areas were performed under the appropriate operations categories (In-Space Vehicle Operations or Planetary Surface Operations). The analysis activities planned for the Science Operations technology areas were deferred to FY90 studies. The remaining activities such as analytic tool development, graphics/video demonstrations and intelligent communicating systems software architecture were performed under the Simulation & Validations category.

Mah, Robert W.↗

Unraveling the relationship between physicochemical properties of NiFeReOx catalysts and the correlated performance toward electrochemical oxygen evolution reaction

NiFeO x catalysts with single site Re dopants exhibit much higher active and stability toward electrochemical oxygen evolution reaction (OER) compared to traditional NiFeO x catalysts. Nevertheless, the relationship between physicochemical properties of NiFeReO x catalysts and the correlated performance toward OER is unclear, which hampers to enhance the OER performance further. Herein, we prepared a series of NiFeReO x catalysts with different physicochemical properties by treating them at different temperatures (up to 350 °C) and then evaluated their performance toward OER. Here, the results show that heat treatment can convert all metal oxidation states to higher values as well as specific surface areas, which are believed to favor real active site generation and OER activity enhancement. A decrease in activity is observed with the temperature increase at the low current range, and the smallest overpotential of 248 mV at 10 mA cm −2 is achieved with the pristine NiFeReO x catalyst. In contrast, the heat-treated samples possess smaller Tafel slopes and lower charge transfer resistance likely due to enhanced intrinsic activity (from higher oxidation states) and conductivity, which facilitate the reaction kinetics and surpass the pristine sample at a large current density. Additionally, the sample treated at 350 °C exhibits a higher activity at 1000 mA cm −2 (1.68 V vs. RHE compared to pristine sample of 1.92 V vs. RHE); however, it manifests a poorer stability compared to the pristine one due to the imbalance of reconstruction/transformations that occurred on the catalyst surface during OER operation. Our work unravels the relationship between physicochemical properties of NiFeReO x catalysts and the correlated OER performance and provides valuable insights for designing NiFeReO x catalysts with high activity and durability.

Catalyst reconstruction↗

Safety and Efficacy of Y-90 Radioembolization After Prior Major Hepatic Resection

PurposeTo evaluate the safety and efficacy of yttrium-90 radioembolization (RE) following left or right hepatic lobectomy.Materials and MethodsBetween 2011 and 2016, 15 patients underwent RE with Y90-resin microspheres following right (8/15) or left (7/15) hepatic lobectomy. In eight patients, the whole liver remnant was treated during a single session, whereas the remaining seven patients received up to 3 selective RE at 1- to 2-month intervals. The administered patient activity was calculated based on the body surface area (BSA) method in all cases. In addition, CT-based volumetry of the liver remnant was performed and used to calculate the absorbed liver dose. Patient follow-up data were retrospectively analyzed regarding signs of radioembolization-induced liver disease (REILD), defined as occurrence of bilirubin >3.0 mg/dl and ascites within 1–2 months after treatment without tumor progression or bile duct occlusion.ResultsThe mean volume of the liver remnant was 1.471 ± 341 ml, the mean administered amount of activity amounted to 1.31 ± 0.74 GBq, and the calculated mean absorbed dose was 42.8 ± 20.6 Gy. The early response to treatment was generally positive, with only one patient showing signs of progressive disease of the treated area on follow-up examinations within the first 2 months post-RE. None of the 15 patients developed a REILD.ConclusionY-90 radioembolization following extended hepatic lobectomy appears to be safe and effective. Although the standard BSA-based dosing seems to suffice to avoid REILD, it results in quite variable liver doses due to variable hypertrophy of the liver remnant post-hepatectomy. Level of Evidence: Level IV, Case series.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

In Situ Studies of Copper-Zirconia-Zinc Oxide Model Catalysts for CO 2 Hydrogenation

A combination of in situ X-ray photoelectron spectroscopy (XPS) and infrared reflection absorption spectroscopy (IRAS) was used to investigate the formation of surface intermediates from CO 2 hydrogenation on copper-zirconia-zinc oxide model catalysts under reaction conditions. Copper clusters with different numbers of atoms (n = 1, 4, 13) were deposited onto bare and ZrO 2 -modified ZnO powder supports to systematically examine the effects of Cu cluster size and the synergy between metal and metal-oxide components. Under low pressure CO 2 hydrogenation conditions (CO 2 :H 2 = 1:9, 0.4 mbar, 300–600 K), XPS and IRAS identify the most prominent intermediates as carbonate (CO 3 *), formate (HCOO*) and methoxy (CH 3 O*), which is the final surface-bound intermediate leading to methanol. The temperature profiles are consistent with a mechanism in which CO 2 is adsorbed as carbonate species (HCO 3 *, CO 3 *) followed by hydrogenation reactions to formate (HCOO*) and methoxy (CH 3 O*), but the relative yields strongly depend on surface composition. Specifically, the presence of ZrO 2 promotes CO 2 adsorption and activation and improves the thermal stability of the Cu clusters against loss of surface area. Moreover, the ternary Cu 4 /ZrO 2 /ZnO surface is significantly more active than Cu 4 /ZnO and ZrO 2 /ZnO surfaces for the formation of methoxy (CH 3 O*), indicating that Cu–ZrO 2 interfaces promote the formation of key intermediates leading to methanol. Finally, the yields of intermediates are similar for all Cu cluster sizes (Cu 1 , Cu 4 and Cu 13 ), indicating that the primary role of Cu is to provide H atoms via H 2 dissociation and spillover. In conclusion, these molecular-level insights provide a fundamental understanding of the enhanced efficiency of ternary Cu–ZrO 2 –ZnO catalysts and establish design principles for developing improved catalysts for CO 2 conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Apollo 15 time and motion study

A time and motion study of Apollo 15 lunar surface activity led to examination of four distinct areas of crewmen activity. These areas are: an analysis of lunar mobility, a comparative analysis of tasks performed in 1-g training and lunar EVA, an analysis of the metabolic cost of two activities that are performed in several EVAs, and a fall/near-fall analysis. An analysis of mobility showed that the crewmen used three basic mobility patterns (modified walk, hop, side step) while on the lunar surface. These mobility patterns were utilized as adaptive modes to compensate for the uneven terrain and varied soil conditions that the crewmen encountered. A comparison of the time required to perform tasks at the final 1-g lunar EVA training sessions and the time required to perform the same task on the lunar surface indicates that, in almost all cases, it took significantly more time (on the order of 40%) to perform tasks on the moon. This increased time was observed even after extraneous factors (e.g., hardware difficulties) were factored out.

Kubis, J. F.↗

Breaking the Linear Scaling Relations for the Oxygen Reduction Reaction with a Dual‐Atom Catalyst Composed of a MnFe‐Porphyrrole Aerogel

Bimetallic catalysts offer enhanced catalytic performance through synergistic interactions between the two metals, allowing them to break the linear scaling relations and reach high electrocatalytic activity. This study presents bimetallic aerogel-based catalyst synthesized as a covalent, three-dimensional framework containing neighboring iron and manganese sites. The aerogel structure provides a high surface area and porosity, facilitating an ultra-high active site density and efficient mass transport. The MnFe porphyrrole's unique structure is obtained by alternately linking Mn-porphyrin and Fe-corrole complexes. It exhibited outstanding performance with an onset potential of 0.99 V RHE . Comparative studies with a free-base Fe porphyrrole catalyst (E onset 0.97 V RHE ) revealed that while Mn incorporation led to only a slight improvement in half-cell performance, it resulted in significantly enhanced performance in anion exchange membrane fuel cell. The MnFe catalyst achieved an OCV of 0.97 V and a peak power density of 0.27 W cm −2 , outperforming the free-base Fe counterpart. Using density functional theory calculations, we show that the higher ORR activity of MnFe-porphyrrole is due to charge transfer between Mn and Fe atoms, which is absent in the reference free-base Fe-porphyrrole. These findings underscore the advantages of bimetallic catalysts in improving ORR activity and fuel cell efficiency by leveraging synergistic effects.

Aerogel↗

Tomographic Imaging of the Suns Interior

A new method is presented of determining the three-dimensional sound-speed structure and flow velocities in the solar convection zone by inversion of the acoustic travel-time data recently obtained by Duvall and coworkers. The initial inversion results reveal large-scale subsurface structures and flows related to the active regions, and are important for understanding the physics of solar activity and large-scale convection. The results provide evidence of a zonal structure below the surface in the low-latitude area of the magnetic activity. Strong converging downflows, up to 1.2 km/s, and a substantial excess of the sound speed are found beneath growing active regions. In a decaying active region, there is evidence for the lower than average sound speed and for upwelling of plasma.

Kosovichev, A. G.↗

Critical Practices in Rigorously Assessing the Inherent Activity of Nanoparticle Electrocatalysts

Accurate activity measurements for electrocatalytic materials are the backbone of impactful electrocatalyst research. Inherent to accurate measurements is the correct accounting of the active catalyst sites and the design of experiments to ensure that these sites are participating in the measured reaction. Improvements in electrocatalyst activity for fuel cell reactions (hydrogen oxidation and oxygen reduction) are essential for the widespread adoption of this carbon-neutral energy source. Activities for these half-reactions can be reported in a variety of ways including specific activities, mass activities, volumetric activities, and half-wave potentials. These values are traditionally measured with a rotating disk electrode (RDE) in which the electrocatalyst is supported on a porous active layer film attached to the RDE. To accurately measure electrocatalyst activity with an RDE, two major sources of errors must be addressed: (i) accurate electrochemical surface area (ECSA) quantification and (ii) fast diffusion of reactants through the active layer film. In this contribution, we first aim to detail through RDE experiments and mass transport modeling the potential errors that can be observed when these factors are not properly addressed. We then present recommendations and discuss techniques for properly constructing electrocatalyst thin films and characterizing the ECSA on monometallic and novel alloy electrocatalysts. These practices, when adopted, ensure greater confidence and reliability in reports of electrocatalyst activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monitoring Depolymerization in Mesopores Using Dynamic Properties of Polymeric Melt Accessed via Dielectric Spectroscopy

Traditional design principles for heterogeneous catalysis guide the use of catalytic particles with mesosized (∼2–50 nm) pores to increase the number of surface-active sites by way of an increased surface area. However, the entry of long-chain polymers into such pores may be significantly limited by the size and entanglement of polymers in the melt state, thereby decreasing the number of accessible sites. Assessment of catalyst performance from traditional reactor-based studies averages over intrapore reaction events as well as reactions on the surface of a particle, resulting in an inability to distinguish between differences in site accessibility and activity. Techniques that assess the intrapore performance can inform the design of future heterogeneous catalysts for polymer upcycling. In this work, we demonstrate the use of broadband dielectric spectroscopy to monitor depolymerization of a polymer melt within mesopores via changes in the segmental relaxation time scale of amorphous polymer chains. In particular, we highlight the use of an anodic aluminum oxide (AAO) membrane as a readily available model for catalyst pores with a well-characterized pore morphology. The decrease in the segmental relaxation (α-relaxation) time of the melt with increasing chain scission emerges as a measure of the extent of polymer deconstruction inside mesopores. To demonstrate the utility of this technique, we demonstrate the decomposition of two commercial poly(propylene carbonate) polymers with different decomposition rates within mesopores. As the polymers depolymerize, their segmental relaxation time decreases as the molecular weight decreases (as predicted by the Fox–Flory equation). The BDS-measured change in segmental relaxation time mirrors the expected trend based on change in molecular weight measured by size exclusion chromatography.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗