Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ambiguities”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Calorimetric Study of Mixed Phosphates Na 4 M 3 (PO 4 ) 2 P 2 O 7 (M = Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ ) to Evaluate the Electrochemical Trends

Mixed polyanionic compounds have been studied extensively as viable cathode materials for sodium-ion batteries. Mixed phosphates, Na 4 M 3 (PO 4 ) 2 P 2 O 7 (M = Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ ), provide a low barrier for Na-ion diffusion, being advantageous in comparison to phosphates and pyrophosphates. The reported order of sodium extraction is ambiguous and remains unclear. Despite being structurally similar, electrochemical performance differs for all four analogues with different degrees of (de)sodiation, according to the transition element present. High-temperature oxide melt solution calorimetry has been used to establish the relation between thermodynamic phase stability and observed capacity for this series of mixed phosphates. Thermodynamic phase stability largely depends on the kind of structure, type of bonding, and size of the cations present. So, according to our results, the thermodynamic phase stability follows the order Na 4 Mn 3 (PO 4 ) 2 P 2 O 7 > Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 > Na 4 Co 3 (PO 4 ) 2 P 2 O 7 > Na 4 Ni 3 (PO 4 ) 2 P 2 O 7 . The thermodynamic studies serve as guidelines for the selection of compositions with the potential for fabricating advanced cathode materials with maximum performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Stabilization of Preternatural Barium Oxidation States as an Unexpected Byproduct of β-Decay: Discovery of a New Halide Semiconductor Alloy

137 Cs has a wide range of roles in the nuclear industry. The solid material, safely encapsulated in CsCl as 137 CsCl, is stored as fission product waste from nuclear power production and legacy waste from nuclear weapons production; it has also served as a radiation source in food and sewage irradiators as well as medical devices. However, because of the solubility of the chloride salt and the relatively high specific activity of 137 Cs, damaged or broken capsules can lead to severe radiological accidents. Safe capsule design and material recycling are complicated by the unclear structural evolution during β-decay, which remains ambiguous due to the differing oxidation states of Cs (1+) and Ba (2+). Here, in this study, we use first-principles calculations to investigate the evolving structure–property relationships of Cs 1–x Ba x Cl during β-decay. Despite the well-established 2+ formal oxidation state of alkali-earth metals, we find that Ba 1+ can be stabilized in the form of a mixed-valence alloy at low concentrations. Specifically, we identify three regimes for the β-decay of 137 Cs into CsCl: Ba-doped CsCl (Ba ≤ 14%), wherein Ba has the expected 2+ oxidation state; Cs–Ba–Cl alloys, where Ba has a mix of the usual Ba 2+ and highly unusual Ba 1+ oxidation state in the form of a quasi-disordered mixed-valence alloy (Ba = 25%); and phase separation into a CsCl + BaCl 2 + Ba (m) mechanical mixture, where Ba reverts to its expected 2+ oxidation state (Ba > 25%). Surprisingly, the Cs 0.75 Ba 0.25 Cl mixed-valence alloy is a narrow indirect band gap semiconductor (1.05 eV) despite the insulating nature of both CsCl and BaCl 2 . It also exhibits strongly excitonic polarized optical properties, has glass-like ultralow thermal conductivity (directional average of 0.21 W/mK at 300 K), and shows greater resistance to deformation under both tensile and volumetric strengths compared with the original CsCl structure (e.g., shear and Young’s modulus of 9.04 and 31.62 GPa, respectively). These findings imply that transmutation of 137 Cs leads to highly unusual chemical bonding that stabilizes Ba 1+ in local regions of the quasi-disordered Cs 0.25 Ba 0.75 Cl, resulting in anomalous physical properties. Moreover, this discovery provides valuable insight for safe nuclear waste capsule design, which can aid in preventing environmental or human exposure to radioactive materials.

Fuhr, Addis S. [Oak Ridge National Laboratory (ORN↗
DOE OSTI2024

IsoForma: An R Package for Quantifying and Visualizing Positional Isomers in Top-Down LC-MS/MS Data

Proteoforms, the different forms of a protein with sequence variations including post-translational modifications (PTMs), execute vital functions in biological systems such as cell signaling and epigenetic regulation. Precisely defining the stoichiometry of PTMs has been challenging because, in the widely used bottom-up proteomics methods, the detection occurs at the peptide level and thus the link between peptides and their specific modification site is lost, resulting in proteoform ambiguity. Advances in top-down mass spectrometry (MS) technology have permitted the direct characterization of intact proteoforms and their exact number of modification sites, allowing for the relative quantification of positional isomers (PI). Proteins with positional isomers refers to proteoforms with identical total mass and set of modifications but varying PTM site combinations. The relative abundance of PI can be estimated by matching proteoform-specific fragment ions to top-down tandem MS (MS2) data to localize and quantify modifications. However, current approaches heavily rely on manual annotation. Here, we present IsoForma, an open-source R package for relative quantification of PI within a single tool. We benchmarked IsoForma’s performance against two existing workflows and highlight the similarity of the results and improvements in speed. Overall, IsoForma provides a streamlined process, reduces the time of conducting isoform-based analyses, and offers an essential framework for developing customized proteoform analysis workflows. Finally, the software is open source and available at https://github.com/EMSL-Computing/isoforma-lib.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Detailed Characterization of an Annealed Reduced Graphene Oxide Catalyst for Selective Peroxide Formation Activity

Recently, electrochemical hydrogen peroxide (H 2 O 2 ) generation from oxygen molecules has been extensively studied. Thus far, the best peroxide activity under alkaline conditions has been reported at the surface of a mild reduced graphene oxide annealed at 600 °C (mrGO-600). However, the detailed material information, such as chemical functionality and structural morphology, is unknown, which results in ambiguous debates on its catalytic active sites. Therefore, to solve this problem, we intensively characterize the structure of mrGO-600 to clarify the origin of its catalytic activity. Various characterizations, including X-ray photoelectron spectroscopy, Raman spectroscopy, infrared spectroscopy, near-edge X-ray absorption fine spectroscopy, and high-resolution transmittance electron microscopy coupled with in situ infrared spectroelecrochemistry, reveal that the annealing process generates not only various hole edge defects that are related to the ring ether group but also numerous point defects that result in a small-sized disconnected graphitic carbon region. These defects are believed to form a unique atomic level configuration in mrGO-600, which enables it to facilitate high peroxide-generated activity from oxygen molecules in an alkaline electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Morphological Degradation of Oxygen Evolution Reaction-Electrocatalyzing Nickel Selenides at Industrially Relevant Current Densities

We investigated electrodeposited nanoparticulate nickel selenide (pre)catalysts that transform into nickel oxides/ oxyhydroxides under oxygen evolution reaction conditions in alkaline solutions. Previous studies of this transformation were conducted at lower current densities than those of industrial relevance (≥1 A cm −2 ). We used ultramicroelectrodes (UMEs) to achieve such current densities, benefiting from their small size, ensuring low absolute currents and low ohmic drop but high current densities. Morphological degradation of the catalyst material was only observed at current densities exceeding 1 A cm −2 but not for smaller ones. Using X-ray absorption, Xray photoemission spectroscopy, and X-ray diffraction, we confirmed that the degradation was accompanied by the literature-known transformation of nanoparticulate Ni 3 Se 2 (bulk)/NiSe (surface) into nickel oxyhydroxide. The transformation of the precatalyst goes along with a significant improvement in the charge transfer kinetics observed by decreasing Tafel slopes with ongoing experimental time extracted from cyclic voltammetry (CV) experiments and electrochemical impedance spectroscopy (EIS) in the high-frequency range. However, these kinetic improvements are accompanied by limitations in mass transport concluded from decreasing current responses at high overpotentials in CVs and increasing impedance in the low-frequency range of the EIS spectra after extended CV cycling. These mass transport limitations originated from morphological degradations at the UME exceeding 1 A cm −2 which we proved by applying identical location scanning electron microscopy. This has not been reported in studies that have been limited to lower current densities before. Our findings showcase how UMEs can be used to study (pre)catalysts (herein nickel selenides) under current densities of industrial relevance in the absence of ohmic drop-related ambiguities, combined with in-depth materials characterization studies, e.g., identical location microscopy and advanced spectroscopic methods. This approach enables direct evaluation and comparison of catalyst materials and thus demonstrates how to overcome long-standing limitations of electrocatalyst design and testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Node-Solution Microenvironment Governs the Selectivity of Thioanisole Oxidation within Catalytic Zr-Based Metal–Organic Framework

Lewis acidic metal oxides, including zirconia (ZrO 2 ), are catalytically active toward oxidative reactions in the presence of sacrificial oxidants like t-butyl hydroperoxide (TBHP). The structural ambiguity and heterogeneity of the ZrO 2 surface impose challenges to chemists in understanding the reaction mechanism down to atomic-level precision. The inorganic, Zr-oxo nodes of many crystalline metal–organic frameworks (MOFs) structurally mimic ZrO 2 . Herein, we report three novel findings: (A) Zr-based MOF, Zr-MOF-808 is catalytically competent in activating TBHP to induce oxygen atom transfer (OAT) reactions to a model substrate, thioanisole, at room temperature, (B) its reaction mechanism can be derived with greater structural precision owing to the crystallinity of the MOF, and (C) the node-binding agent and other reaction conditions significantly impact the selectivity between the singly oxidized methyl phenyl sulfoxide vs the doubly oxidized sulfone. These findings suggest that both the activity and selectivity of OAT reactions within Zr-MOF-808 are governed by the chemistry occurring at the interface of the node and the surrounding reaction medium. Implications of these findings in OAT reactions and other MOF/metal oxide-catalyzed relevant catalysis are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Propane Dehydrogenation Catalyzed by Supported Group IV (Ti, Zr, Hf) Organometallics on Silicon Nitride

Mesoporous silicon nitride (Si 3 N 4 ) enables access to chemisorbed group IV organometallics catalysts active for propane dehydrogenation (PDH) compared to the organometallic analogues on mesoporous silica under the same reaction conditions. The series of Si 3 N 4 -supported materials are active catalysts, (Zr > Hf > Ti k f = 290, 232, and 162 mol mol Metal -1 h -1 at 450 °C with 2% C 3 H 8 in Ar, respectively) with selectivity above 95%, demonstrating additional examples of Ti and Hf systems for PDH. However, the underlying mechanism of the improved performance relative to oxide supported homologues is not well-understood. Characterization of thermally treated samples (DRIFTS, XAS and SSNMR) and computational modeling of this catalyst series was utilized to differentiate between potential amido - (C-H activation along the M-N bond) and imido - (C-H activation along the M=N bond) mechanisms. Due to remaining mechanistic ambiguity, a Ga analogue was synthesized and evaluated for PDH activity as an indirect probe to experimentally differentiate pathways. An inversion of the oxide/nitride performance trend is observed for the Ga congener which does not form a Ga=N bond, most consistent with different mechanisms dictating the performance of the group IV/Si 3 N 4 catalysts vs Ga/Si 3 N 4 .

heterolytic cleavage↗
DOE OSTI2020

Chemical Imaging of Fine Mode Atmospheric Particles Collected from a Research Aircraft over Agricultural Fields

Vegetation and crops in agricultural areas are a significant source of both biogenic secondary organic aerosols and of directly emitted primary biological atmospheric particles (PBAPs) composed of plant fragments/debris, fungal spores, pollen, and bacteria among others. Seasonal crop harvesting significantly intensifies regional PBAP emissions and aerosolizes soil organic matter and dust particulates. In this paper, the atmospheric contributions and impact of PBAPs have been insufficiently investigated due to limited real-time observations and ambiguity in their detection by existing measurement techniques. We collected ambient particles on-board an instrumented Beechcraft BE76 Duchess research aircraft flying above actively harvested agriculture fields of corn and soybean crops. In this work, particle samples were analyzed using complementary chemical imaging techniques, including computer-controlled scanning electron microscopy coupled with elemental microanalysis to describe particle-type population and scanning transmission X-ray microscopy to provide quantitative metrics on particle internal heterogeneity. We show the particle-class contribution is consistent between corn and soybean harvesting across altitudes of 100–300 m AGL. The contribution of PBAPs in the size range of 0.15–1.25 μm is estimated to be 10–12% of ~39,000 analyzed particles. Determining viscosity with X-ray microanalysis has shown that the fine-mode organic particles collected are viscous/semisolid (10 2 –10 12 Pa s) while the majority of PBAP fragments are solid (>10 12 Pa s). The observation of submicrometer, solid carbonaceous fragments of biogenic origin has implications for the regional cloud condensation nuclei and ice nuclei budget. Therefore, seasonal harvesting of crops may play an important, yet unrecognized, role in regional cloud formation and climate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Experimental Protocols for Studying Organic Non-aqueous Redox Flow Batteries

We report that Redox flow batteries (RFBs) are promising devices for grid-scale energy storage due to the decoupling of power and energy, which can be independently scaled by the electrode area and storage tank size, respectively. To date, only aqueous RFBs, such as the vanadium RFB, have been implemented commercially. Nevertheless, the limited energy densities and high-cost materials may preclude their wider market penetration. Organic non-aqueous redox-flow batteries (O-NRFBs), which utilize redox-active organic molecules (ROMs), have been offered as an attractive alternative. Many possible advantages include the use of earth-abundant elements (C, H, N, O, S, F), wherein the ROMs can be prepared from low-cost and sustainable materials. Additionally, a large variety of electroactive moieties are accessible as building blocks, providing a synthetic platform to tune the properties of ROMs through rational design. As a consequence, the development of novel ROMs has attracted researchers with diverse backgrounds, prompting remarkable innovations in the past decade. However, consistency in experimental protocols (e.g., electrochemical methods, cycling stability, experimental conditions) has not coincided with this uptick in research, leading to sometimes ambiguous and incomparable results. This is further convoluted by the complexity innate to battery development, such as cell design, detection, and characterization of reactions and active components. The O-NRFB application imposes stringent requirements on the physical or/and chemical processes involved in electrochemical cycling. Yet such considerations are often overlooked. Further, while quantum mechanical calculations provide a convenient tool for evaluating and selecting ROM candidates, this simulation is not always performed. Thus, in this Energy Focus, we detail a means to standardize experimental protocols for studies of O-NRFBs and suggest practices to facilitate fundamental understanding and development of ROMs.

25 ENERGY STORAGE↗
DOE OSTI2024

Spatial Progression of Polysulfide Reactivity with Lithium Nitrate in Li–Sulfur Batteries

LiNO 3 is a commonly used electrolyte additive in Li-S batteries, but the intricacies of its stabilizing effect on these batteries are not well-understood due to the complex chemical nature of Li-S electrolytes. This complexity often hampers clear characterization and interpretation of data. In this study, we explore the reactivity of LiNO 3 in Li-S batteries through in operando sulfur K-edge spectroscopy. To remove ambiguities, a sulfur-free electrolyte with LiNO 3 as the sole salt is used. This allows a precise elucidation of the reaction mechanism between LiNO 3 and polysulfides. Here, we observe that the reaction is chemical in nature and progresses spatially, influenced by the polysulfide concentration gradient across the electrolyte. Polysulfides are electrochemically generated in situ on the cathode side, leading to high local concentration. As a result, they cannot be fully oxidized by LiNO 3 and forms sulfites initially which are gradually further oxidized into sulfonates and sulfates. Conversely, polysulfides on the anode side have lower local concentration as they are not generated in situ but diffused from the cathode side. Their reaction with LiNO 3 leads to highly oxidized species like sulfonates and sulfates. These reaction products are not reduced during electrochemically cycling, suggesting their capabilities of passivating the electrodes and contributing to the cycle stabilities of Li-S batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Surfactant-Mediated Growth and Patterning of Atomically Thin Transition Metal Dichalcogenides

The role of additives in facilitating the growth of conventional semiconducting thin films is well-established. Apparently, their presence is also decisive in the growth of two-dimensional transition metal dichalcogenides (TMDs), yet their role remains ambiguous. In this work, we show that the use of sodium bromide enables synthesis of TMD monolayers via a surfactant-mediated growth mechanism, without introducing liquefaction of metal oxide precursors. We discovered that sodium ions provided by sodium bromide chemically passivate edges of growing molybdenum disulfide crystals, relaxing in-plane strains to suppress 3D islanding and promote monolayer growth. To exploit this growth model, molybdenum disulfide monolayers were directly grown into desired patterns using predeposited sodium bromide as a removable template. In conclusion, the surfactant-mediated growth not only extends the families of metal oxide precursors but also offers a way for lithography-free patterning of TMD monolayers on various surfaces to facilitate fabrication of atomically thin electronic devices.

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

Ion Correlations Decrease Particle Aggregation Rate by Increasing Hydration Forces at Interfaces

The connection between solution structure, particle forces, and emergent phenomena at solid–liquid interfaces remains ambiguous. In this case study on boehmite aggregation, we established a connection between interfacial solution structure, emerging hydration forces between two approaching particles, and the resulting structure and kinetics of particle aggregation. In contrast to expectations from continuum-based theories, we observed a nonmonotonic dependence of the aggregation rate on the concentration of sodium chloride, nitrate, or nitrite, decreasing by 15-fold in 4 molal compared to 1 molal solutions. These results are accompanied by an increase in repulsive hydration forces and interfacial oscillatory features from 0.27–0.31 nm in 0.01 molal to 0.38–0.52 nm in 2 molal. Moreover, molecular dynamics (MD) simulations indicated that these changes correspond to enhanced ion correlations near the interface and produced loosely bound aggregates that retain electrolyte between the particles. In conclusion, we anticipate that these results will enable the prediction of particle aggregation, attachment, and assembly, with broad relevance to interfacial phenomena.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tailoring MoS 2 for Small-Molecule Electroreduction: The Role of Metal Doping and Heterostructures

The electrification of chemical transformations central to sustainable fuel production and waste valorization, such as overall water splitting (OWS), hydrogen evolution reaction (HER), and electrochemical reduction of CO 2 (CO 2 R), presents a powerful opportunity to advance carbon-neutral energy technologies. Transition metal dichalcogenides (TMDs), particularly MoS 2 , have emerged as promising electrocatalyst candidates, owing to their abundance, tunable active sites, and defect-rich structures. This review highlights recent progress in leveraging metal doping and heterostructure engineering of MoS 2 to enhance the electrocatalytic activity and selectivity. By compiling insights from experimental studies and density functional theory (DFT) predictions, we examine how defect creation, electronic structure modification, and interface design contribute to improved charge transport and catalytic efficiency. Particular emphasis is placed on rational design principles, synthetic strategies, and operando characterization methods that provide a pathway to understanding and optimizing MoS 2 -based materials. We also discuss the challenges of stability, mechanistic ambiguity, and scaling while outlining opportunities to bridge theory and experiment. Collectively, this review underscores how defect and heterostructure engineering of MoS 2 can accelerate the development of efficient, sustainable electrocatalysts for both fuel generation and waste-to-value generation.

CO2 reduction↗
DOE OSTI2020

Nicotine Monitoring with a Wearable Sweat Band

The tobacco epidemic is a public health threat that has taken a heavy toll of lives around the globe each year. Smoking affects both the smokers and those who are exposed to secondhand smoke, and careful tracking of exposure can be key to mitigating the potential hazards. For smokers, the variation of chemical compositions between commercial cigarettes has led to ambiguity in estimating the health risks, both for active smokers and others involuntarily exposed to tobacco smoke and byproducts. In this regard, sweat possesses an attractive opportunity to monitor smoke exposure due to sweat's abundance in biomolecules and its great accessibility. In this paper, we present a wearable sweat band to monitor nicotine, a prominent ingredient in cigarettes, as a viable way to quantitatively assess a wearer's exposure to smoking. Both smokers and normal subjects are tested to demonstrate the use of this device for smoke-related health monitoring. Our results exhibit confirmable and elevated nicotine levels in sweat for subjects inhaling cigarette smoke. This continuous and personalized sweat sensing device is leverage to monitor smoke pollution for a potentially broad population.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Deconvoluting Structures of Component Plant Biopolymers Using Deuterium Labeled Brassica oleracea Stems

Several Brassica species are cultivated globally for the production of seed oils as food, lubricants, and increasingly biofuels. The stem and leaf residues of these herbaceous dicotyledonous crops constitute another feedstock for biofuels and other products. Plant cell walls are complex, multipolymeric structures that consist primarily of polysaccharides and lignin. Cellulose chains coalesce to form crystalline microfibrils while the amorphous biopolymers, hemicellulose, and lignin form a network structure and fill the interstitial space. Neutron scattering has been used for the structural study of the assembly and deconstruction of the plant cell walls. However, similar neutron sensitivity of the different amorphous biopolymers has made structural association to individual component biopolymers nontrivial and ambiguous. To improve the association of structural features to specific biopolymer components, partial deuteration of the plant cell wall can be employed to increase the difference in the neutron scattering length density between amorphous carbohydrate and lignin plant polymers. Vegetative stems from partially deuterated Brassica oleracea acephala (kale) plants were obtained commercially, and the plant cell wall structures were studied by contrast-variation small-angle neutron scattering (CV-SANS) and Fourier-transform infrared spectroscopy (FTIR). FTIR results indicated that deuterium substitution for hydrogen in the carbohydrates was higher than that in lignin. By combining CV-SANS and FTIR results, the neutron scattering length density (nSLD) of the polysaccharides and lignin was determined to match nSLD of 65%:35% and 48%:52% D 2 O/H 2 O solvent mixtures, respectively. These nSLD values were higher than the nSLD values of polysaccharides and lignin for H 2 O grown biopolymers. The nSLD increase correlates to replacing about 42.5% of hydrogens present as both C–H and O–H groups in cellulose with deuterium atoms, while only 21% for lignin. In conclusion, this study lays the foundation to use partially deuterated plants to deconvolute structural features of the different component biopolymers, especially cellulose, hemicellulose, and lignin, of the plant cell wall without introducing unintended structural modifications due to the pretreatment extraction processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Adjusting the Criteria for Hydrogen Evolution by Single-Atom Catalysts

Downsizing noble metal catalysts is essential for improving atomic efficiency in sustainable energy applications. Typically, strategies focus on anchoring atomically scaled catalysts onto heteroatom-rich substrates, but these interactions can unintentionally alter the electronic structure of the catalyst, complicating the hydrogen evolution reaction (HER) mechanism. This study focuses on elucidating the interfacial mechanism of HER using structurally well-defined platinum single-atom (Pt SA) electrocatalysts. Unlike chemically reduced SAs, electrochemically deposited Pt SA catalysts do not rely on strong support interactions. As a result, these isolated Pt atoms can potentially achieve the theoretical maximum hydrogen production efficiency. This work introduces electrocatalysts composed solely of true SA sites, clarifying previous ambiguities surrounding the concept of SA electrocatalysis.

adsorption↗
DOE OSTI2026

Mechanism of Tyrosine-Driven Deprotonation in Photosystem II Revealed by Multiscale Simulations

Photosystem II (PSII) drives light-induced water oxidation via stepwise redox transitions of its oxygen-evolving complex (OEC), a Mn 4 Ca cluster advancing through five intermediate S-states (S 0 –S 4 ). The S 2 → S 3 transition involves a redox event in which a Mn ion donates an electron to the redox-active tyrosine YZ, coupled to deprotonation of an OEC-bound water ligand─yet the underlying coupling mechanism remains unresolved. Time-resolved serial femtosecond crystallography (TR-SFX) has revealed transient electron density shifts near the redox-active tyrosine Y Z , interpreted as sequential oxidation and reduction, with reduction initiating ∼1 μs after excitation and substantially progressed by 30 μs. However, this interpretation conflicts with kinetics from photothermal beam deflection (PBD), time-resolved X-ray absorption spectroscopy (TR-XAS), and electron paramagnetic resonance (EPR), which place electron transfer at 190–400 μs and proton transfer around 30 μs. Here, we reconcile these discrepancies using quantum mechanics/molecular mechanics (QM/MM) and molecular dynamics (MD) simulations. We show that oxidation of P680 and Y Z breaks the symmetry of the nearby hydrogen bonds involving water molecule W4, displacing Y Z and replicating the TR-SFX features of Y Z and Q165 observed at 1 μs. This local perturbation propagates through a hydrogen-bond network, transmitting the electrostatic signal from Y Z to the E65-E312 dyad and triggering redox-coupled deprotonation via the Cl1 channel. By 30 μs, the hydrogen-bond symmetry is restored through deprotonation of W2 (or alternatively W1), reproducing the disappearance of TR-SFX density differences around Y Z and Q165 without requiring Y Z reduction. Our proposed mechanism also gives molecular insights into the O6* density, assigning it to water reorganization rather than a discrete Ca-bound hydroxide species. Here, our results reveal a detailed atomistic mechanism linking Y Z oxidation to long-range proton release and suggest a functional role for the nearby Cl – ion in proton transfer. More broadly, this study underscores the importance of hydrogen-bond dynamics in mediating redox-driven proton transport and demonstrates how integrative simulations can resolve mechanistic ambiguities.

Deprotonation↗
DOE OSTI2024

Unraveling the Luminescence Quenching Mechanism in Strong and Weak Quantum-Confined CsPbBr 3 Triggered by Triarylamine-Based Hole Transport Layers

Luminescence quenching by hole transport layers (HTLs) is one of the major issues in developing efficient perovskite light-emitting diodes (PeLEDs), particularly prominent in blue-emitting devices. While a variety of material systems have been used as interfacial layers, the origin of such quenching and the type of interactions between perovskites and HTLs are still ambiguous. Here, we present a systematic investigation of the luminescence quenching of CsPbBr 3 by a commonly employed hole transport polymer, Poly(9,9-dioctylfluorene-alt-N-(4-sec-butylphenyl)-diphenylamine) (TFB) in LEDs. Strong and weakly quantum-confined CsPbBr 3 (nanoplatelets (NPLs)/nanocrystals (NCs)) are rationally selected to study the quenching mechanism by considering the differences in their morphology, energy level alignments, and quantum confinement. The steady-state and time-resolved Stern-Volmer plots unravel the dominance of dynamic and static quenching at lower and higher concentrations of TFB, respectively, with maximum quenching efficiency of 98%. The quenching rate in NCs is faster than in NPLs owing to their longer PL lifetimes and weak quantum confinement. The ultrafast transient absorption results support these dynamics and rule out the involvement of Forster or Dexter energy transfer. Finally, the 1D 1 H and 2D NOESY NMR study confirms the exchange of native ligands at the NCs surface with TFB, leading to dark CsPbBr 3 -TFB ensemble formation accountable for luminescence quenching. This highlights the critical role of the triarylamine functional group on TFB (also the backbone of many HTLs) in the quenching process. These results shed light on the underlying reasons for the luminescence quenching in PeLEDs and will help to choose the interfacial layers rationally for developing efficient LEDs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗