Results for “Critical Step” — Page 3

NASA NTRS2024

Experimental Studies on the Effect of Impact Processes on the Formation and Evolution of Amino Acids

Introduction: A critical step in the emergence of life on Earth was the synthesis of larger organic molecules from simple building blocks such as NH3, CO2, H2O, and CH3OH. The presence of amino acids and other complex organics in comets and meteorites demonstrates that widespread organic synthesis likely occurred across the early solar system. Building on previous work [e.g., 1-3], we systematically explore impact-driven chemical evolution of exogenous organics and their precursors. Collisional processes may also have provided a source of energy for the formation of more complex organics from endogenous building blocks. The high flux of impactors to Earth immediately prior to and during the origins of life suggests that impacts could have played a critical role. Key Questions: 1. How are the formation and evolution of amino acids affected by the presence of a mineral matrix during cometary and asteroidal impacts onto the early Earth? 2. Do some minerals (e.g., phyllosilicates) provide a more robust protective framework or reactive surface site for amino-acid formation and/or polymerization? 3. Does the abundance of ices and/or amino acids relative to that of the mineral matrix affect the formation and evolution of amino acids? 4. Are there impact velocities/shock pressures at which formation or polymerization of amino acids is favored or precluded? Experimental Approach: This study systematically examines the conditions under which amino acids and other organic molecules can form, be polymerized, and/or be destroyed during impact events into particulate regolith simulants. Variable parameters include the modal composition of this regolith (silicate matrices, ratios of ices, silicates, and amino acids) and impact velocities/shock pressures. Impacts experiments were performed using the two-stage light-gas gun (LGG), vertical gun (VG), and flat-plate accelerator (FPA) in the Experimental Impact Lab at JSC. FPA experiments were performed over a range of shock pressures (11.3-31.5 GPa) using CM chondrite simulant mixed with amino acids at ratios of 0:10, 1:10, 1:103, and 1:106 (amino acid:host). Techniques for mixing cometary ices have been optimized and test runs have been performed using the LGG (see figure below). Analysis: Post-impact, samples are heated in water to extract amino acids and peptides. Extracts are characterized via liquid chromatography-mass spectrometry (LC-MS) and the mineralogies of solid residues are characterized using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Additional LC-MS and mineralogical analyses are underway.

Eve L Berger↗

DOE OSTI2026

Origin of Electrochemical Activation Leading to Enhanced Cycling Stability of Li‐ and Mn‐Rich Cathodes

Electrochemical activation is a critical step for optimal functioning of Li- and Mn-rich (LMR) cathodes, yet the underlying mechanism for such activation remains elusive. Here, by using scanning/transmission electron microscopy (S/TEM) combined with the associated energy-dispersive x-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS), we decipher the origin of the activation enhanced electrochemical properties. We reveal that activation induces the formation of a spinel-like phase within the C2/m domains of the LMR cathode, where the transition-metal ions partially occupy both the tetrahedral (8a) and octahedral (16c) sites of the $Fd\bar{3}m$ spinel lattice, distinguishing the spinel-like phase from the conventional high-voltage spinel. Systematic varying the cycling voltage reveals a critical activation voltage above which this spinel-like phase forms, while lower voltages preserve the layered bulk structure. As the spinel-like phase is a stable structure for electrochemical cycling, the present findings provide direct mechanistic insight into the voltage-dependent activation process and explain how the C2/m to spinel-like transformation upon activation contributes to the electrochemical performance of LMR cathodes, providing guidance for the rational design of Li-rich cathodes with enhanced cycling durability.

Li-rich and Mn-rich cathode↗

DOE OSTI2021

Computation of linear MHD instabilities with the multi-region relaxed MHD energy principle

Over the last decade, a variational principle based on a generalisation of Taylor's relaxation, referred to as multi-region relaxed magnetohydrodynamics (MRxMHDs) has been developed. The numerical solutions of the MRxMHD equilibria have been constructed using the Stepped Pressure Equilibrium Code (SPEC) (Hudson et al 2012 Phys. Plasmas 19 112502). In principle, SPEC could also be established to describe the MRxMHD stability of an equilibrium. In this work, a theoretical framework is developed to relate the second variation of the energy functional to the so-called Hessian matrix, enabling the prediction of MHD linear instabilities of cylindrical plasmas, and is implemented in SPEC. The negative and positive eigenvalues of the Hessian matrix predict the stability of an equilibrium. Verification studies of SPEC stability results with the M3D-C 1 code and the tearing mode $\Delta^{^{\prime}}$ criterion have been conducted for ideal and resistive MHD instabilities, respectively, in a pressureless cylindrical tokamak, and have shown good agreement. Overall, our stability analysis is a critical step towards understanding the MHD stability of three-dimensional MHDs where nested flux surfaces, magnetic islands and stochastic regions co-exist.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2003

Tracking capability for entry, descent and landing and its support to NASA Mars Exploration Rovers

This paper described a new capability recently deployed in the NASA Deep Space Network to support the entry, descent and landing of the two Mars Exploration Rovers - Spirit and Opportunity. This final segment of a 7-month journey was critical step in enabling successful mission operation. The EDL Data Analysis (EDA) equipment processed the open loop recording samples from the existing radio science receivers, extracted the MFSK-modulated tones, and provided information on the occurrence of associated events happened onboard spacecraft. The EDA software supported real-time as well as post pass processing. The design flexibility allowed the track to be divided into different segments, each could be processed with a configuration optimized for its signal conditions and uncertainties. The use of dynamic lock state concept enabled signal detection be done with minimum required computing power - less was spent when signal was steadily detected and more when signal fluctuated. With the server-client design, the EDA supported connections to different remote operation centers for monitor purpose. The paper also presented the field results from both Spirit and Opportunity landings. The detection were much better than anticipated. All critical event tones were seen in real time. Surprising detection of LCP signal was found with Spirit landing, resulted in a reconfiguration for Opportunity landing to maximize signal detection.

tracking↗

NASA NTRSDate not supplied

Hot Water, Cold Reality: Experimental Analysis of Sorption Constraints in Iodine Filtration Media Under Heated-Water Conditions

Iodine has been widely employed as a residual biocide in potable water applications during crewed missions. Unlike other biocides, it is essential to remove iodine from drinking water prior to consumption, as its biocidal concentration raises health concerns. Consequently, effectively removing iodine species from water is a critical step in potable water processing. Although the non-biocided heated leg has not violated microbial specifications on the International Space Station, any wetted volume lacking biocide presents potential risks for long‑duration exploration missions and for systems that are sensitive to microbial growth/contamination. Recent assessments indicate, however, that iodine‑removal performance may degrade under elevated temperature conditions, such as those required for dispensing hot water for food preparation. This reduction in efficacy appears to stem from both the potential physical degradation of filtration media and the temperature‑dependent behavior of adsorption processes. To investigate the influence of water temperature on the efficacy of filtration media for iodine removal, a series of adsorption capacity tests were conducted at both room temperature and elevated temperatures (90 °C). These experiments aimed to benchmark the performance of the adsorbents that constitute the ACTEX filter in the ISS’s potable water dispenser. The findings of this study provide critical insights into the iodine filtration process, verify the potential performance shortfall under elevated temperature conditions, and establish the basis for defining new absorbent requirements to ensure reliable iodine removal in future mission architectures.

iodine↗

NASA NTRSDate not supplied

Hot Water, Cold Reality: Experimental Analysis of Sorption Constraints in Iodine Filtration Media Under Heated-Water Conditions

Iodine has been widely employed as a residual biocide in potable water applications during crewed missions. Unlike other biocides, it is essential to remove iodine from drinking water prior to consumption, as its biocidal concentration raises health concerns. Consequently, effectively removing iodine species from water is a critical step in potable water processing. Although the non-biocided heated leg has not violated microbial specifications on the International Space Station, any wetted volume lacking biocide presents potential risks for long‑duration exploration missions and for systems that are sensitive to microbial growth/contamination. Recent assessments indicate, however, that iodine‑removal performance may degrade under elevated temperature conditions, such as those required for dispensing hot water for food preparation. This reduction in efficacy appears to stem from both the potential physical degradation of filtration media and the temperature‑dependent behavior of adsorption processes. To investigate the influence of water temperature on the efficacy of filtration media for iodine removal, a series of adsorption capacity tests were conducted at both room temperature and elevated temperatures (90 °C). These experiments aimed to benchmark the performance of the adsorbents that constitute the ACTEX filter in the ISS’s potable water dispenser. The findings of this study provide critical insights into the iodine filtration process, verify the potential performance shortfall under elevated temperature conditions, and establish the basis for defining new absorbent requirements to ensure reliable iodine removal in future mission architectures.

drinking water↗

NASA NTRS2023

Spacesuit Fit and Mobility Assessments by Digital Human Modeling

Spacesuit Fit and Mobility Assessments by Digital Human Modeling K. Han Kim (Leidos, Inc.) Elizabeth A. Benson (KBR, Inc.) Sudhakar L. Rajulu (NASA Johnson Space Center) Spacesuits are required to accommodate safe operations for astronauts across gender and a wide variety of body shapes and sizes. This goal has been of particular importance given the increasing diversity of NASA crewmembers for upcoming Missions. While testing with design prototypes is a critical step for spacesuit development, iterative mockup design, fabrication, and human subject tests can be extremely costly and time consuming. Moreover, testing with a limited subject pool has often raised questions for validity, as test subjects need to represent the entire astronaut population, not only of the past or current, but also the future. This study is aimed at demonstrating how digital human modeling (DHM) tools have been built and directly supported NASA spacesuit developments. With DHM, the computer aided design (CAD) model of a spacesuit was integrated with human body models. Two use scenarios are presented in this paper, namely fit and mobility. For fit assessments, the suit-to-body contact and compression patterns were estimated using 3D human body scan models virtually wearing a spacesuit model. A statistical fit classifier was made from the contact patterns and applied against a large database of body scans (N=2,500). With this technique, the NASA reference design spacesuit Exploration EVA Mobility Unit (xEMU)was verified to accommodate 90% of the astronaut-like population, with the critical dimensions covering 1stto 99thpercentiles of the target body measurements. A similar technique assessed XEMU mobility. The maximum reach envelopes were considered, within which the work objects and critical hardware interfaces should be located for safe and ergonomic operations. While the reach envelope geometry varies significantly with the suit wearer’s body size and strength, the existing test data did not include the subjects critically required to define suit mobility requirements, such as very small females or large males. Using the xEMU virtual model kinematically simulated and permuted for a hypothetical wearer, however, the existing data were statistically transformed and scaled. This method enabled for a parametric estimation of the reach envelopes from the 1stpercentile female or 99thpercentile male. The outcome was successfully incorporated for requirement developments. With the new DHM tools, human integration of the spacesuit was structurally simulated and predictively assessed, which would have been otherwise impossible. Also, the needs for iterative mockup and subject tests were significantly reduced, which resulted in time and cost saving. Additional work is in progress to integrate additional vehicles, tools, and hardware with DHM framework.

K Han Kim↗

NASA NTRS2020

Enabling Dynamic Vehicle Analyses With Improved Atmospheric Attenuation Models in Glenn Research Center Communication Analysis Suite

To aid in meeting the NASA objective of returning humans to the Moon, the Glenn Research Center’s Communication Analysis Suite was augmented with two distinct capabilities. The first capability added was the vehicle propagator. This allows the addition of dynamic aircraft and ground vehicles around any celestial body within the solar system during an analysis. This functionality interpolates the position and velocity of the vehicle relative to a celestial body at the time steps analyzed using the type of path and either a series of waypoints or a direction and duration of travel. The implications of this new capability include lunar rovers and/or drones, such as Dragonfly, where the vehicle propagator will analyze the communications architecture. The newly created vehicle propagator is now in use in communications studies for the 2024 lunar missions, simulating the movement of lunar rovers across the Moon’s southern pole. The second capability added was the augmentation of the atmospheric attenuation model. The previous model did not have a uniform low-elevation attenuation model due to the trigonometric approximation for path length and the exponential nature of low-elevation scintillation. User-defined weather parameters were also added to the updated atmospheric attenuation model. The previous model solely used tabular data based upon the season and location of the transmitting antenna. Multiple simulations of the same configuration now return different results based on the differing weather parameters. Cognitive communications analysis efforts can use this second capability to generate neural network training data based on differing weather conditions at utilized ground stations, a critical step in allowing neural networks to learn how weather parameters impact communications performance.

vehicle propagation↗

DOE OSTI2025

Advanced defrosting techniques in air source heat pumps: A review of vapor injection, thermal energy storage, and experimental frost accumulation data

Electrification is a critical step for reducing greenhouse gas emissions from heating. Air source heat pumps (ASHPs) are a promising alternative to fossil fuel-based systems due to their high coefficients of performance (COP), dual heating and cooling capability, and lower carbon footprint. However, for ASHPs to achieve widespread adoption, they must operate reliably across all climates, including cold regions. Additionally, defrosting techniques should be energy efficient and minimally disruptive to indoor comfort. Vapor injection (VI) technology can address the high-pressure and high-temperature lift challenges encountered in low ambient conditions. More recently, in addition to enhancing heating performance, VI has also been shown to improve the speed and efficiency of reverse cycle defrosting. Likewise, thermal energy storage (TES) has steadily gained attention for its ability to serve as an auxiliary heat source during both normal operation and defrosting. This review analyzes the benefits and limitations of VI- and TES-assisted defrosting approaches. While both technologies show strong potential individually, no studies to date have explored their combined use in ASHP systems. Additionally, to support continued development of defrosting strategies, both in modeling and experimental work, it is critical to establish frost accumulation data under a range of operating conditions. By compiling the available data from the literature, this paper also highlights the limited availability of such experimental data and the wide variation in frosting and defrosting durations and termination criteria, which are often influenced by system design and test setups.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2025

Propane Activation on Pt Electrodes at Room Temperature: Quantification of Adsorbate Identity and Coverage

Abstract C−H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon‐intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low‐temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products. Herein, we utilize a combination of electrochemical mass spectrometry (ECMS) and density functional theory (DFT) calculations to elucidate the potential dependence of propane activation on Pt electrocatalysts. Results show a strong dependence of adsorption on the applied potential in room‐temperature aqueous acidic electrolyte, with a maximum coverage of propane‐derived adsorbates at 0.30 V vs RHE. Using charge deconvolution and deuterated experiments, the mechanism of adsorption was elucidated, and C 3 H 2 * was determined as the average dehydrogenated propane‐derived adsorbate species. DFT calculations further corroborate these results, showing that the formation of deeply dehydrogenated species is energetically accessible at room temperature. The combined theoretical and experimental findings yield insights for selective activation of paraffinic C−H bonds at room temperature, aqueous conditions—a critical step towards decarbonized chemical manufacturing.

Chemistry↗

NASA NTRS2021

Separation at Crossing Waypoints Under Wind Uncertainty in Urban Air Mobility

To enable high-density operations in major metropolitan areas, urban air mobility networks are anticipated to have air traffic management with higher levels of autonomy. To ensure that this type of autonomy is feasible, one of the critical steps from a safety and efficiency perspective is understanding various factors that affect the spatial separation between airborne flights and ensure that these factors can be managed. In terms of separation assurance and scheduling, an important real-world concern is that future states of aircraft cannot be perfectly predicted. The focus of this research paper is to understand how these prediction errors affect separation and scheduling services and to explore mitigation strategies to handle these errors. In this research, we have simulated these types of uncertainty by adding wind-prediction errors to trajectory predictions for separation. With these wind-prediction errors, we decompose the problem into two separate questions. First, using both simulation and analytical methods, we look at conflict-detection-only scenarios to understand how the wind errors affect required minimum temporal separation between crossing flights to ensure a specific spatial separation. Next, we study how trajectory errors effect conflict resolution, and we explore different combinations of scheduling and separation assurance to mitigate the effects of uncertainty between crossing flights. The conflict resolution algorithm aims to minimize necessary temporal separation between crossing flights under uncertainty, still ensuring safety-critical spatial separation. In summary, this research suggests that the required minimum temporal separation at a crossing waypoint is dependent on factors such as inbound crossing angle, the relative angle between wind direction and bearing of each route, wind magnitude, wind magnitude uncertainty, nominal cruise airspeed of aircraft, and look-ahead time of the conflict detection algorithm. This research also suggests that different combinations of scheduling and separation have different qualitative results. Using a combination of strategic, flow-based scheduling, tactical scheduling at crossings, speed control near crossing points, and separation management leads to a system that is insensitive to trajectory prediction errors with high throughput and flexibility for aircraft away from shared resources.

urban air mobility↗

NASA NTRS2021

Separation at Crossing Waypoints Under Wind Uncertainty in Urban Air Mobility

To enable high-density operations in major metropolitan areas, urban air mobility networks are anticipated to have air traffic management with higher levels of autonomy. To ensure that this type of autonomy is feasible, one of the critical steps from a safety and efficiency perspective is understanding various factors that affect the spatial separation between airborne flights and ensure that these factors can be managed. In terms of separation assurance and scheduling, an important real-world concern is that future states of aircraft cannot be perfectly predicted. The focus of this research paper is to understand how these prediction errors affect separation and scheduling services and to explore mitigation strategies to handle these errors. In this research, we have simulated these types of uncertainty by adding wind-prediction errors to trajectory predictions for separation. With these wind-prediction errors, we decompose the problem into two separate questions. First, using both simulation and analytical methods, we look at conflict-detection-only scenarios to understand how the wind errors affect required minimum temporal separation between crossing flights to ensure a specific spatial separation. Next, we study how trajectory errors effect conflict resolution, and we explore different combinations of scheduling and separation assurance to mitigate the effects of uncertainty between crossing flights. The conflict resolution algorithm aims to minimize necessary temporal separation between crossing flights under uncertainty, still ensuring safety-critical spatial separation. In summary, this research suggests that the required minimum temporal separation at a crossing waypoint is dependent on factors such as inbound crossing angle, the relative angle between wind direction and bearing of each route, wind magnitude, wind magnitude uncertainty, nominal cruise airspeed of aircraft, and look-ahead time of the conflict detection algorithm. This research also suggests that different combinations of scheduling and separation have different qualitative results. Using a combination of strategic, flow-based scheduling, tactical scheduling at crossings, speed control near crossing points, and separation management leads to a system that is insensitive to trajectory prediction errors with high throughput and flexibility for aircraft away from shared resources.

urban air mobility↗

DOE OSTI2021

Unlocking the secret of lignin-enzyme interactions: Recent advances in developing state-of-the-art analytical techniques

Bioconversion of renewable lignocellulosics to produce liquid fuels and chemicals is one of the most effective ways to solve the problem of fossil resource shortage, energy security, and environmental challenges. Among the many biorefinery pathways, hydrolysis of lignocellulosics to fermentable monosaccharides by cellulase is arguably the most critical step of lignocellulose bioconversion. In the process of enzymatic hydrolysis, the direct physical contact between enzymes and cellulose is an essential prerequisite for the hydrolysis to occur. However, lignin is considered one of the most recalcitrant factors hindering the accessibility of cellulose by binding to cellulase unproductively, which reduces the saccharification rate and yield of sugars. This results in high costs for the saccharification of carbohydrates. The various interactions between enzymes and lignin have been explored from different perspectives in literature, and a basic lignin inhibition mechanism has been proposed. However, the exact interaction between lignin and enzyme as well as the recently reported promotion of some types of lignin on enzymatic hydrolysis is still unclear at the molecular level. Multiple analytical techniques have been developed, and fully unlocking the secret of lignin-enzyme interactions would require a continuous improvement of the currently available analytical techniques. This review summarizes the current commonly used advanced research analytical techniques for investigating the interaction between lignin and enzyme, including quartz crystal microbalance with dissipation (QCM-D), surface plasmon resonance (SPR), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), nuclear magnetic resonance (NMR) spectroscopy, fluorescence spectroscopy (FLS), and molecular dynamics (MD) simulations. Interdisciplinary integration of these analytical methods is pursued to provide new insight into the interactions between lignin and enzymes. Finally, this review will serve as a resource for future research seeking to develop new methodologies for a better understanding of the basic mechanism of lignin-enzyme binding during the critical hydrolysis process.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2020

3D Hybrid Plasmonic Framework with Au Nanopillars Embedded in Nitride Multilayers Integrated on Si

Integration of nanoscale photonic and plasmonic components on Si substrates is a critical step toward Si-based integrated nanophotonic devices. Herein, a set of unique complex 3D metamaterials with intercalated nanolayered and nanopillar structures with tunable plasmonic and optical properties on Si substrates is designed. More specifically, the 3D metamaterials combine metal (Au) nanopillars and alternating metal-nitride (Au-TiN and Au-TaN) nanolayers, epitaxially grown on Si substrates. The ultrafine Au nanopillars ( d ≈ 3 nm) continuously grow throughout all the nanolayers with high epitaxial quality. Novel optical properties, such as highly anisotropic optical property, high absorbance covering the entire visible spectrum regime, and hyperbolic property in the visible regime, are demonstrated. Furthermore, a waveguide based on a silicon nitride (Si 3 N 4 ) ridge with a multilayer structure is successfully fabricated. The demonstration of 3D nanoscale metamaterial design integrated on Si opens up a new route toward tunable metamaterials nanostructure designs with versatile material selection for various optical components in Si integrated photonics.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Layered Transition Metal Oxides as Ca Intercalation Cathodes: A Systematic First-Principles Evaluation

Finding high-voltage Ca cathode materials is a critical step to unleashing the full potential of high-energy-density Ca-ion batteries. Therefore, first-principles calculations are used to demonstrate that P-type layered calcium transition metal (TM) oxide materials (CaTM 2 O 4 ) with a range of TM substitutions (TM = Ti, V, Cr, Mn, Fe, Co, and Ni) have excellent battery-related properties including thermodynamic stability, average voltage, energy density, synthesizability, ionic mobility, and electronic structure. However, the thermodynamic stability of the charged phase and TM redox activity are shown to be sensitive to TM selection, with CaCo 2 O 4 having the best balance of all considered properties. The utility of combining multiple TMs to expand the chemical search space for TM substitutions is demonstrated by mixing Co and Ni in layered CaTM 2 O 4 .

25 ENERGY STORAGE↗

DOE OSTI2023

High-Throughput Automated Exploration of Phase Growth Behaviors in Quasi-2D Formamidinium Metal Halide Perovskites

Quasi-2D metal halide perovskites (MHPs) are an emerging material platform for sustainable functional optoelectronics, but the uncontrollable, broad phase distribution remains a critical challenge for applications. Nevertheless, the basic principles for controlling phases in quasi-2D MHPs remain poorly understood, due to the rapid crystallization kinetics during the conventional thin-film fabrication process. In this work, a high-throughput automated synthesis-characterization-analysis workflow is implemented to accelerate material exploration in formamidinium (FA)-based quasi-2D MHP compositional space, revealing the early-stage phase growth behaviors fundamentally determining the phase distributions. Upon comprehensive exploration with varying synthesis conditions including 2D:3D composition ratios, antisolvent injection rates, and temperatures in an automated synthesis-characterization platform, it is observed that the prominent n = 2 2D phase restricts the growth kinetics of 3D-like phases—α-FAPbI 3 MHPs with spacer-coordinated surface—across the MHP compositions. Thermal annealing is a critical step for proper phase growth, although it can lead to the emergence of unwanted local PbI 2 crystallites. Additionally, fundamental insights into the precursor chemistry associated with spacer-solvent interaction determining the quasi-2D MHP morphologies and microstructures are demonstrated. The high-throughput study provides comprehensive insights into the fundamental principles in quasi-2D MHP phase control, enabling new control of the functionalities in complex materials systems for sustainable device applications.

2D perovskites↗

DOE OSTI2021

Characterization of a Molecule Partially Confined at the Pore Mouth of a Zeotype

Abstract We investigate the interaction between a molecule and a pore mouth—a critical step in adsorption processes—by characterizing the conformation of a macrocyclic calix[4]arene‐Ti IV complex, which is grafted on the external surface of a zeotype (*‐SVY). X‐ray absorption and 13 C{ 1 H} CPMAS NMR spectroscopies independently detect a unique conformation of this complex when it is grafted at crystallographically equivalent locations that lie at the interface of 7 Å hemispherical microporous cavities and the external surface. Electronic structure calculations support the presence of this unique conformation, and suggest that it is brought about by a specific orientation of the macrocycle that maximizes non‐covalent interactions between calix[4]arene upper‐rim tert ‐butyl substituents and the microporous‐cavity walls. Our comparative study provides a rare “snapshot” of a molecule partially confined at a pore mouth, an essential intermediate for adsorption into micropores, and demonstrates how surrounding environment controls this confinement in a sensitive fashion.

Grosso‐Giordano, Nicolás A.↗

DOE OSTI2023

Low Catalyst Loading Enhances Charge Accumulation for Photoelectrochemical Water Splitting

Abstract Solar water oxidation is a critical step in artificial photosynthesis. Successful completion of the process requires four holes and releases four protons. It depends on the consecutive accumulation of charges at the active site. While recent research has shown an obvious dependence of the reaction kinetics on the hole concentrations on the surface of heterogeneous (photo)electrodes, little is known about how the catalyst density impacts the reaction rate. Using atomically dispersed Ir catalysts on hematite, we report a study on how the interplay between the catalyst density and the surface hole concentration influences the reaction kinetics. At low photon flux, where surface hole concentrations are low, faster charge transfer was observed on photoelectrodes with low catalyst density compared to high catalyst density; at high photon flux and high applied potentials, where surface hole concentrations are moderate or high, slower surface charge recombination was afforded by low‐density catalysts. The results support that charge transfer between the light absorber and the catalyst is reversible; they reveal the unexpected benefits of low‐density catalyst loading in facilitating forward charge transfer for desired chemical reactions. It is implied that for practical solar water splitting devices, a suitable catalyst loading is important for maximized performance.

Liu, Tianying↗