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DOE OSTI2017

Marcus Theory of Ion-Pairing

We present a theory for ion pair dissociation and association, motivated by the concepts of the Marcus theory of electron transfer. Despite the extensive research on ion-pairing in many chemical and biological processes, much can be learned from the exploration of collective reaction coordinates. To this end, we explore two reaction coordinates, ion pair distance and coordination number. The study of the correlation between these reaction coordinates provides a new insight into the mechanism and kinetics of ion pair dissociation and association in water. The potential of mean force on these 2D-surfaces computed from molecular dynamics simulations of different monovalent ion pairs reveal a Marcus-like mechanism for ion-pairing: Water molecules rearrange forming an activated coordination state prior to ion pair dissociation or association, followed by relaxation of the coordination state due to further water rearrangement. Like Marcus theory, we find the existence of an inverted region where the transition rates are slower with increasing exergonicity. This study provides a new perspective for the future investigations of ion-pairing and transport. SR, CJM, and GKS were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS3 (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). The research was performed using PNNL Institutional Computing. PNNL is a multi-program national laboratory operated by Battelle for the U.S. Department of Energy.

Roy, Santanu↗

DOE OSTI2016

Reaction Rate Theory in Coordination Number Space: An Application to Ion Solvation

Understanding reaction mechanisms in many chemical and biological processes require application of rare event theories. In these theories, an effective choice of a reaction coordinate to describe a reaction pathway is essential. To this end, we study ion solvation in water using molecular dynamics simulations and explore the utility of coordination number (n = number of water molecules in the first solvation shell) as the reaction coordinate. Here we compute the potential of mean force (W(n)) using umbrella sampling, predicting multiple metastable n-states for both cations and anions. We find with increasing ionic size, these states become more stable and structured for cations when compared to anions. We have extended transition state theory (TST) to calculate transition rates between n-states. TST overestimates the rate constant due to solvent-induced barrier recrossings that are not accounted for. We correct the TST rates by calculating transmission coefficients using the reactive flux method. This approach enables a new way of understanding rare events involving coordination complexes. We gratefully acknowledge Liem Dang and Panos Stinis for useful discussion. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. SR, CJM, and GKS were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS3 (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.

Roy, Santanu↗

DOE OSTI2024

FEW questions, many answers: using machine learning to assess how students connect food–energy–water (FEW) concepts

There is growing support and interest in postsecondary interdisciplinary environmental education which integrate concepts and disciplines in addition to providing varied perspectives. There is a need to assess student learning in these programs as well as rigorous evaluation of educational practices, especially of complex synthesis concepts. This work tests a text classification machine learning model as a tool to assess student systems thinking capabilities using two questions anchored by the Food-Energy-Water (FEW) Nexus phenomena by answering two questions (1) Can machine learning models be used to identify instructor-determined important concepts in student responses? (2) What do college students know about the interconnections between food, energy and water, and how have students assimilated systems thinking into their constructed responses about FEW? Reported here are a broad range of model performances across 26 text classification models associated with two different assessment items, with model accuracy ranging from 0.755 to 0.992. Expert-like responses were infrequent in our dataset compared to responses providing simpler, incomplete explanations of the systems presented in the question. For those students moving from describing individual effects to multiple effects, their reasoning about the mechanism behind the system indicates advanced systems thinking ability. Specifically, students exhibit higher expertise for explaining changing water usage than discussing tradeoffs for such changing usage. This research represents one of the first attempts to assess the links between foundational, discipline-specific concepts and systems thinking ability. These text classification approaches to scoring student FEW Nexus Constructed Responses (CR) indicate how these approaches can be used, in addition to several future research priorities for interdisciplinary, practice-based education research. Development of further complex question items using machine learning would allow evaluation of the relationship between foundational concept understanding and integration of those concepts as well as more nuanced understanding of student comprehension of complex interdisciplinary concepts.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗

DOE OSTI2020

Accelerated Charged Particle Tracking with Graph Neural Networks on FPGAs

We develop and study FPGA implementations of algorithms for charged particle tracking based on graph neural networks. The two complementary FPGA designs are based on OpenCL, a framework for writing programs that execute across heterogeneous platforms, and hls4ml, a high-level-synthesis-based compiler for neural network to firmware conversion. We evaluate and compare the resource usage, latency, and tracking performance of our implementations based on a benchmark dataset. We find a considerable speedup over CPU-based execution is possible, potentially enabling such algorithms to be used effectively in future computing workflows and the FPGA-based Level-1 trigger at the CERN Large Hadron Collider.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2018

Elementary Steps of Faujasite Formation Followed by in Situ Spectroscopy

Ex situ and in situ spectroscopy was used to identify the kinetics of processes during the formation of the faujasite (FAU) zeolite lattice from a hydrous gel. Using solid-state 27Al MAS NMR, the autocatalytic transformation from the amorphous gel into the crystalline material was monitored. Al-XANES shows that most Al already adopts a tetrahedral coordination in the X-ray-amorphous aluminosilicate at the beginning of the induction period, which hardly changes throughout the rest of the synthesis. Using 23Na NMR spectroscopy, environments in the growing zeolite crystal were identified and used to define the processes in the stepwise formation of the zeolite lattice. The end of the induction period was accompanied by a narrowing of the 27Al and 23Na MAS NMR peak widths, indicating the increased long-range order. The experiments show conclusively that the formation of faujasite occurs via the continuous formation and subsequent condensation of intermediary sodalite-like units that constitute the key building block of the zeolite. Acknowledgement The authors thank T. Huthwelker for assistance with XAFS experiment setup at the Swiss Light Source (PSI, Switzerland). Further, we would like to acknowledge V. Shutthanandan and B.W. Arey for performing Helium ion microscopy as well as Z. Zhao, N.R. Jaeger, M. Weng, C. Wan and M. Hu for aiding in the NMR experimental procedure. T. Varga is acknowledged for his help with the capillary XRD. A.V., D.M.C., J.H., J.L.F and J.A.L. were supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. S.P. and M.A.D. acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL. The in situ NMR experiments were supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences. Part of the research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

faujasite↗

DOE OSTI2020

Applying cumulative effects to strategically advance large-scale ecosystem restoration

Programs restoring large terrestrial-aquatic ecosystems are expected to increase in area and number over the next decade. Factors ensuring long-term effectiveness at the program scale differ from those at the individual restoration project scale, necessitating a new synthesis. Here we contextualize hydrological, geomorphological, and biological effects of large-scale ecosystem restoration activities within a cumulative-effects paradigm. Evidence of eight modes of cumulative effects benefiting species and ecosystems was elucidated by reviewing restoration efforts in the greater Florida Everglades, Gulf Coast, lower Columbia River and estuary, Puget Sound estuary, Missouri River, northeastern coastal states, San Francisco Bay and Sacramento Delta. Additive and nonlinear cumulative effects of interacting restoration projects propagated across landscape and regional geographic scales, and throughout trophic levels, affecting population structures. Applying a cumulative-effects paradigm to planning, implementing, and evaluating large-scale restoration will avoid countervailing effects and capitalize on positive feedback, advancing evidence-based programs to recover priority species and ecosystems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2017

Sub-micron Cu/SSZ-13: Synthesis and application as selective catalytic reduction (SCR) catalysts

Not Available

Prodinger, Sebastian (ORCID:0000000187490476)↗

DOE OSTI2023

Symmetry-Breaking Dendrimer Synthons in Colloidal Crystal Engineering with DNA

Breaking symmetry in colloidal crystals is challenging due to the inherent chemical and structural isotropy of many nanoscale building blocks. If a non-particle component could be used to anisotropically encode such building blocks with orthogonal recognition properties, one could expand the scope of structural and compositional possibilities of colloidal crystals beyond what is thus far possible with purely particle-based systems. In this work, we report the synthesis and characterization of novel DNA dendrimers that function as symmetry-breaking synthons, capable of programming anisotropic and orthogonal interactions within colloidal crystals. When the DNA dendrimers have identical sticky ends, they hybridize with DNA-functionalized nanoparticles to yield three distinct colloidal crystals, dictated by dendrimer size, including a structure not previously reported in the field of colloidal crystal engineering, Si 2 Sr. When used as symmetry-breaking synthons (when the sticky ends deliberately consist of orthogonal sequences), the synthesis of binary and ternary colloidal alloys with structures that can only be realized through directional interactions is possible. Furthermore, by modulating the extent of shape anisotropy within the DNA dendrimers, the local distribution of the nanoparticles within the crystals can be directed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

ARCS: Agentic Retrieval-Augmented Code Synthesis with Iterative Refinement

Agentic Retrieval-Augmented Code Synthesis with Iterative RefinementIn supercomputing, efficient and optimized code generation is essential to leverage high-performance systems effectively. We have developed Agentic Retrieval-Augmented Code Synthesis (ARCS), an advanced framework for accurate, robust, and efficient code generation, completion, and translation. ARCS integrates Retrieval-Augmented Generation (RAG) with Chain-of-Thought (CoT) reasoning to systematically break down and iteratively refine complex programming tasks. An agent-based RAG mechanism retrieves relevant code snippets, while real-time execution feedback drives the synthesis of candidate solutions. This process is formalized as a state-action search tree optimization, balancing code correctness with editing efficiency. Evaluations on the Geeks4Geeks and HumanEval benchmarks demonstrate that ARCS significantly outperforms traditional prompting methods in translation and generation quality. By enabling scalable and precise code synthesis, ARCS offers transformative potential for automating and optimizing code development in supercomputing applications, enhancing computational resource utilization

Bhattarai, Manish [Los Alamos National Labs]↗

DOE OSTI2021

Composable Programming of Hybrid Workflows for Quantum Simulation

We present a composable design scheme for the development of hybrid quantum/classical algorithms and workflows for applications of quantum simulation. Our object-oriented approach is based on constructing an expressive set of common data structures and methods that enable programming of a broad variety of complex hybrid quantum simulation applications. The abstract core of our scheme is distilled from the analysis of the current quantum simulation algorithms. Subsequently, it allows a synthesis of new hybrid algorithms and workflows via the extension, specialization, and dynamic customization of the abstract core classes defined by our design. We implement our design scheme using the hardware-agnostic programming language QCOR into the QuaSiMo library. To validate our implementation, we test and show its utility on commercial quantum processors from IBM, running some prototypical quantum simulations.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2018

Impact of Structural Defects and Hydronium Ion Concentration on the Stability of Zeolite BEA in Aqueous Phase

The presence of fluoride anions in the synthesis gel leads to zeolite BEA with high hydrothermal stability. This longer lifetime is caused by a lower concentration of internal silanol defects that are sites of the initial framework hydrolysis eventually destroying the lattice structure. The lifetime of these zeolites was the higher the lower the concentration of framework bridging hydroxyl groups that form hydronium ions was. While lattice hydrolysis was initiated at defect sites in all cases, the role of defects became less important as the concentration of hydronium ions increased. At higher concentration of hydrated hydronium ions, the presence of water associated with the hydrated hydronium ions limits the useful lifetime of zeolite catalysts in water. For such materials, the selective hydrophobization of the external surface extends the lifetime. Acknowledgments: S.P. and M.A.D. acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL. H.S. and H.W. were supported by the Chemical Transformation Initiative (CTI) conducted under Laboratory Directed Research & Development Program at PNNL. J.A.L. was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences.

Prodinger, Sebastian↗

DOE OSTI2019

The Diverse Nature of Ion Speciation at the Nanoscale Hydrophobic/Water Interface

Herein we investigate ion pairing at weakly charged hydrophobic/water interfaces. In particular, the speciation of the thiocyanate (SCN-) ion in the vicinity of the nano aqueous (NaSCN solution) - hydrophobic (dodecane) interface in the presence of tetraalkylammonium groups attached to dodecyl chains (DTA+). This combined simulation and experimental approach finds that the SCN- interfacial ion pairs already form at concentrations as low as 5 mM and exist in three distinct, detectable structural motifs controlled by the SCN- concentration in the aqueous phase. The first is the association with the DTA+, followed by hydrophobic adsorption to the interface with the sulfur end of the SCN-, followed by an oppositely aligned SCN- absorption with a solvated nitrogen end of the SCN-. These different structures are formed due to subtle shifts in interactions and their elucidation requires multiple surface sensitive measurements in conjunction with the description of the interface using a representation of the interactions with quantum density functional theory (DFT). Together, this study reveals that we can both simultaneously control and detect subtle changes in the speciation of ions in the vicinity of soft interfaces. This work is supported by the Julia Jacobi Foundation and the European Research Council (grant number 616305). Christopher J. Mundy is supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES) Division of Chemical Sciences, Geosciences, and Biosciences. Marcel D. Baer is supported within the Materials Synthesis and Simulation Across Scales (MS3) Initiative through the Laboratory Research and Development Program at Pacific Northwest National Laboratory (PNNL). The calculations utilized resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US DOE under Contract No. DE-AC02-05CH11231. PNNL is a multiprogram national laboratory operated by Battelle for the US DOE.

Zdrali, Evangelia↗

DOE OSTI2015

Impact of zeolite aging in hot liquid water on activity for acid-catalyzed dehydration of alcohols

The catalytic performance of zeolite in aqueous medium depends on a multitude of factors, such as the concentration and distribution of active sites and framework integrity. Al K–edge extended X–ray absorption fine structure and 27Al MAS NMR spectroscopies in combination with DFT calculations are used to determine the distribution of tetrahedral Al sites both qualitatively and quantitatively for both parent and 48 h 160 ºC water treated HBEA catalysts. There is no evidence of Al coordination modification after aging in water. The distribution and concentration of Al T–sites, active centers for the dehydration of cyclohexanol, do not markedly impact the catalytic performance in water, because the Brønsted acidic protons are present in the form of hydrated hydronium ions and thus have very similar acid properties. The results suggest that all Brønsted acid sites are equally active in aqueous medium. The decrease of zeolite catalytic performance after water treatment is attributed to the reduced concentration of Brønsted acid sites. Increasing the stability of pore walls and decreasing the rate of Si–O–Si group hydrolysis may result in improved apparent zeolite catalytic performance in aqueous medium. Authors thank B. W. Arey (PNNL) for HIM measurements, T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland), J. Z. Hu and S. D. Burton (PNNL) for support during NMR experiments. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MD acknowledges support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL. HIM imaging and NMR experiments were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE Office of Science, Office of Biological and Environmental Research, located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle Memorial Institute under contract # DE-AC05-76RL0-1830

alcohol dehydration↗

DOE OSTI2016

Improving Stability of Zeolites in Aqueous Phase via Selective Removal of Structural Defects

This work reports significant improvement in the hydrothermal stability of a well-characterized BEA zeolite via the selective removal of structural defects. Recent work suggests that the presence of silanol defects destabilizes the framework integrity of most zeolites and makes them susceptible to hydrolysis of the siloxy bonds by hot liquid water. The described approach allows for a key removal of silanols as shown with 29Si-MAS-NMR. Subsequently, the material stability in hot liquid water, measured by retention of its crystallinity with X-ray diffraction (XRD), is found to be superior to defective zeolites. In addition, N2-sorption measurements (BET) and transmission electron microscopy (TEM) show the formation of different types of mesoporosity for water-treated stabilized and unmodified materials. While the sorption capacity for untreated materials drops, related to re-precipitation of dissolved silica and pore blocking, the stabilized material retains its microporosity and improves its overall sorption capacity. The authors would like to thank B. W. Arey (PNNL) for HIM measurements and I. Arslan for TEM imaging. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. SP and MD acknowledge support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2013

SECA Coal-Based Systems - LGFCS

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2014

SECA Coal-Based Systems - LGFCS

LGFCS is developing an integrated planar (IP) SOFC technology for mega-watt scale power generation including the potential for use in highly efficient, economically competitive central generation power plant facilities fuel by coal synthesis gas. This Department of Energy Solid-State Energy Conversion Alliance (SECA) program has been aimed at achieving further cell and stack technical advancements and assessing the readiness of the LGFCS SOFC stack technology to be scaled to larger-scale demonstrations as a path to commercialization. Significant progress was achieved in reducing to practice a higher performance and lower cost cell technology, identifying and overcoming degradation mechanisms, confirming the structural capability of the porous substrate for reliability, maturing the strip design for improved flow to allow high fuel utilization operation while minimizing degradation mechanisms and obtaining full scale block testing at 19 kW under representative conditions for eventual product and meeting SECA degradation metrics. The SECA program has played a key role within the overall LGFCS development program in setting the foundation of the technology to justify the progression of the technology to the next level of technology readiness testing.

Goettler, Richard↗

DOE OSTI2021

Solar Photovoltaic Module Recycling: A Survey of U.S. Policies and Initiatives

Industry stakeholders, regulators, and policymakers in the United States are starting to develop policies for PV module recycling. Well-designed policies could reduce negative environmental impacts and resource constraints while opening new market and employment opportunities. This paper summarizes drivers, barriers, and enablers related to PV module recycling, which might be addressed via policy. It then analyzes existing and proposed U.S. policies that may affect PV module recycling. Among the global and national voluntary industry stewardship standards related to EoL PV management, this paper discusses a Solar Energy Industries Association program encouraging PV recycling among its U.S. membership. The paper concludes with a synthesis of policy-related factors that may encourage effective EoL PV module management.

14 SOLAR ENERGY↗

DOE OSTI2017

Synthesis and Crystal Structures of Volatile Neptunium(IV) β- Diketonates

Production of certified reference materials in support of domestic nuclear forensics programs require volatile precursors for introduction into electromagnetic isotopic separation instruments. β-diketone chelates of tetravalent actinides are known for their high volatility, but previously developed synthetic approaches require starting material (NpCl 4 ) that is prohibitively difficult and hazardous to prepare. An alternative strategy was developed here that uses controlled potential electrolysis to reduce neptunium to the tetravalent state in submolar concentrations of hydrochloric acid. Four different β-diketone ligands of varying degrees of fluorination were reacted with an aqueous solution of Np 4+ . Products of this reaction were characterized via X-ray diffraction and infrared spectroscopy, and were found to be neutral 8-coordinate complexes that adopt square antiprismatic crystal geometry. Synthesis of Np β-diketonates by this approach circumvents the necessity of using NpCl 4 in tetravalent Np coordination compound synthesis. The volatility of the complexes was assessed using thermogravimetric analysis, where the temperature of sublimation was determined to be in the range of 180° to 205° C. The extent of fluorination did not appreciably alter the sublimation temperature of the complex. Thermal decomposition of these compounds was not observed during sublimation. High volatility and thermal stability of Np β-diketonates make them an ideal candidate for gaseous introduction into isotopic separation instruments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗