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At least 757 records · Page 42

Center for Gas Separations (CGS)

The total energy consumption in the U.S. has been rising steadily for decades, and it currently amounts to ~98,000 TBtu/yr, with approximately 30% of this total attributable to the industrial sector. Reasonable estimates indicate that 45–55% of total industry energy consumption derives from chemical separations, and for example, over 120 TBtu/yr alone is used in carrying out olefin/paraffin separations via energy-intensive cryogenic distillation. Therefore, the pursuit of new, even radically different approaches to some of the most energy-intensive industrial separations processes is an imperative scientific pursuit for reducing energy consumption toward a more sustainable future. Adsorbent and membrane-based separations can require a fraction of the energy needed for distillation methods, and as such are considered promising solutions for balancing increasing energy demand in the U.S. with the need for a massive reduction in energy consumption. Although considerable research effort has been devoted to the design of materials capable of carrying out various gas separations, usually operating through size-selective, chemisorptive, or physisorptive mechanisms, it remains a great challenge to design materials that function adequately for real-world applications. Indeed, the chemical and physical differences between molecules in gas mixtures of interest are often small, and therefore it is necessary, through the use of nanoscience and synthetic chemistry, to engineer unprecedented molecular-level control in adsorbate–adsorbent interactions. The overarching mission of the Center for Gas Separations (CGS) was to discover fundamental innovations that have the potential to dramatically reduce the energy associated with critical gas separations. In particular, the CGS developed novel synthetic routes, guided by molecular chemistry principles, as well as advanced characterization and computational methods, that have enabled the discovery of new materials and membranes tailor-made to exhibit exceptional performance for a range of gas separations processes, as required in the clean use of fossil fuels and in reducing CO 2 emissions from industry. A challenge of this magnitude required the collaboration and synergy of a large team of researchers with expertise in materials synthesis, characterization, and computations. During the 11-year project period, the CGS created a range of new materials within the family of highly-tunable, porous solids known as metal–organic frameworks (MOFs). These new frameworks demonstrate novel mechanisms for key industrial gas separations, including revolutionary new cooperative adsorption processes that enable low-energy CO 2 and CO capture, and are capable of efficiently separating olefins from paraffins, O 2 from air, and the shape-selective separation of alkane isomers. In addition, the CGS developed new strategies for incorporating these materials into composite membranes toward highly efficient and selective membrane-based separations. As a testament to the success of the CGS, two start-up companies, Mosaic Materials,4 Inc. and Flux Technology, Inc., grew out of these research efforts, and these companies are seeking to commercialize MOF and composite membranes materials for key separations in industry, including large-scale CO 2 capture and hydrocarbon separations, respectively. Another company, framergy, Inc., licensed IP resulting from CGS research toward the commercialization of adsorbents for various energy-relevant applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mercury Methylation and Soil Organic Matter Degradation in Incubations with Added Acetate, Isotope-Labeled Mercury, and Selective Microbial Inhibitors, Teller and Council Sites, Seward Peninsula, 2018-2019

This dataset provides the results of laboratory soil microcosm incubation experiments conducted under anaerobic conditions with added acetate, isotope-labeled mercury, and selective microbial inhibitors (2-bromoethanesulfonate and sodium molybdate). The microcosms contained soil collected in August 2018 from the NGEE Arctic Teller Road Site at mile marker 27 (TL_MM27) near Intensive Site 9 (TL_IS_9) and from the Council Road Site (CN_MM71). Incubations were conducted at 8°C for 180 days (Teller incubations) or 60 days (Council incubations). The microcosm headspace was sampled at designated intervals for greenhouse gas concentrations, then destructively harvested and extracted using ultrapure water and 0.1 M KCl for analysis of the porewater geochemistry. This dataset contains one pdf, two csv data files, and one zipped file with raw data.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Era of entropy: Synthesis, structure, properties, and applications of high-entropy materials

The field of high-entropy materials (HEMs) has emerged as a dynamic area of scientific exploration, driven by the exceptional properties arising from their compositional complexity. Encompassing both high-entropy alloys (HEAs) and high-entropy ceramics (HECs), these materials have garnered significant attention across diverse research domains. From investigations into phase evolution and mechanical characteristics to studies of ionic, electronic, and magnetic behaviors, HEMs demonstrate remarkable potential for a wide array of applications. These range from catalysis and tribology to energy storage and superconductivity. Fundamental research has shed light on crucial phenomena such as configurational entropy, lattice distortion, and sluggish diffusion. These discoveries are paving the way for materials design strategies that enable new functional tunability and resistance to application-specific harsh environments. This burgeoning field promises to revolutionize material design and performance across numerous technological sectors. Here, this special collection between Applied Physics Letters and the Journal of Applied Physics provides a timely overview of the latest research in this area. It highlights the growing interest in understanding the impact of high compositional complexity on conventional structure–process–property–performance relationships in HEMs.

36 MATERIALS SCIENCE↗

Coherent-Precipitation-Stabilized Phase Formation in Over-Stoichiometric Rocksalt-Type Li Superionic Conductors

Rationalizing synthetic pathways is crucial for material design and property optimization, especially for polymorphic and metastable phases. Over-stoichiometric rocksalt (ORX) compounds, characterized by their face-sharing configurations, are a promising group of materials with unique properties; however, their development is significantly hindered by challenges in synthesizability. Here, taking the recently identified Li superionic conductor, over-stoichiometric rocksalt Li–In–Sn–O (o-LISO) material as a prototypical ORX compound, the mechanisms of phase formation are systematically investigated. It is revealed that the spinel-like phase with unconventional stoichiometry forms as coherent precipitate from the high-temperature-stabilized cation-disordered rocksalt phase upon fast cooling. This process prevents direct phase decomposition and kinetically locks the system in a metastable state with the desired face-sharing Li configurations. This insight enables us to enhance the ionic conductivity of o-LISO to be >1 mS cm -1 at room temperature through low-temperature post-annealing. This work offers insights into the synthesis of ORX materials and highlights important opportunities in this new class of materials.

36 MATERIALS SCIENCE↗

Plasma-Catalyst Synergy in the One-Pot Nonthermal Plasma-Assisted Synthesis of Aromatics from Methane

Electrification of the methane dehydroaromatization reaction with the use of nonthermal plasmas could alleviate the high-temperature requirement for this process while promoting the formation of valuable aromatics. Here, in this work, we evaluate the use of nonthermal plasma to investigate methane activation and conversion to aromatics by systematically varying bulk gas temperature in a one-pot, plasma-stimulated catalytic reactor over Mo/H-ZSM-5 and metal-free H-ZSM-5 catalysts. We report that Mo is not required for methane activation under low-temperature plasma conditions (573–773 K), and methane conversions up to ~15% with a 1:1 methane/N 2 feed are obtained under a 10 W plasma. However, Mo contributes to the formation of aromatics in the presence of a plasma at 773 K, achieving close to a 2-fold increase in the production of aromatics when compared to unmodified H-ZSM-5. Further, the exposure of as-prepared Mo/H-ZSM-5 to the methane plasma feed induces the formation of Mo-carbide phases in the temperature range studied. These findings highlight the complex roles of nonthermal plasmas in the direct activation of methane and the importance of plasma-catalyst design to facilitate aromatization reactions under plasma-assisted reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic dynamics of gas-dependent oxide reducibility

Understanding oxide reduction is critical for advancing metal production, catalysis and energy technologies. Although carbon monoxide (CO) and hydrogen (H 2 ) are widely used reductants, the mechanisms by which they work are often presumed to be similar, both involving lattice oxygen removal. However, because of growing interest in replacing CO with H 2 to lower CO 2 emissions, distinguishing gas-specific reduction pathways is critical. Yet, capturing these atomic-scale processes under reactive gas and high-temperature conditions remains challenging. Here we use environmental transmission electron microscopy, which is capable of real-time, atomic-resolution imaging of gas–solid redox reactions to directly visualize the gas-dependent oxide reduction dynamics in NiO. We show that CO drives surface nucleation and the growth of metallic Ni islands, leading to self-limiting surface metallization. Conversely, H 2 activates a coupled surface-to-bulk transformation, where protons from dissociated H 2 infiltrate the oxide lattice to promote the inward migration of surface-generated oxygen vacancies and enabling bulk metallization. By contrast, oxygen vacancies formed by CO remain confined near the surface, where they rapidly form a metallic Ni layer that inhibits further reduction. Furthermore, these results reveal distinct atomistic pathways for CO and H 2 and provide insights that may guide metallurgical processes and catalyst design.

36 MATERIALS SCIENCE↗

Carbonate-Catalyzed CO 2 Insertion into Hydrocarbon C-H Bonds (Final Technical Report)

The development of methods to utilize CO 2 as a feedstock for chemical and fuel synthesis is critical for creating renewable alternatives to fossil fuel-based products. This project investigated a class of catalyst materials known as "dispersed carbonates", which are composed of alkali carbonate salts (e.g. potassium carbonate) dispersed in porous support materials. These catalysts react with CO 2 and organic molecules to form chemicals known as carboxylates that have wide applications in the chemical industry. The project used a combination of spectroscopic and reactivity studies to provide fundamental insight into the structure and mechanism of dispersed carbonates in these reactions, leading to variants with greater reactivity. In addition, dispersed carbonates were investigated for CO 2 hydrogenation catalysis, which is critical for processes under development for making sustainable fuels. The dispersed carbonates proved to be highly active and selective catalysts for the reverse water gas shift reaction in which CO 2 is hydrogenated to CO. The dispersed carbonates provide a compelling alternative to conventional metal-based catalysts for reverse water gas shift that could enable new process designs with higher efficiency and lower complexity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Response Surface Methodology for Bi-Level Integrated System Synthesis (BLISS)

The report describes a new method for optimization of engineering systems such as aerospace vehicles whose design must harmonize a number of subsystems and various physical phenomena, each represented by a separate computer code, e.g., aerodynamics, structures, propulsion, performance, etc. To represent the system internal couplings, the codes receive output from other codes as part of their inputs. The system analysis and optimization task is decomposed into subtasks that can be executed concurrently, each subtask conducted using local state and design variables and holding constant a set of the system-level design variables. The subtasks results are stored in form of the Response Surfaces (RS) fitted in the space of the system-level variables to be used as the subtask surrogates in a system-level optimization whose purpose is to optimize the system objective(s) and to reconcile the system internal couplings. By virtue of decomposition and execution concurrency, the method enables a broad workfront in organization of an engineering project involving a number of specialty groups that might be geographically dispersed, and it exploits the contemporary computing technology of massively concurrent and distributed processing. The report includes a demonstration test case of supersonic business jet design.

Altus, Troy David↗

3D Printed Carbon Aerogels for Polymer-Electrolyte Fuel Cells

Carbon aerogels (CA) are known for ultra-low density, very high surface area, fine porous structure, and excellent electrical conductivity. Recent advances in high resolution 3D printing at LLNL enable the manufacturing of complex structured CA electrodes which have been demonstrated in electrolysis, flow battery, and supercapacitor applications. Polymer-electrolyte fuel cells (PEFC) may be an excellent candidate for these materials/methods as designers seek to optimize membrane-electrode assemblies to achieve higher efficiencies. A major challenge to PEFC design is two-phase flow due to water production which causes pore flooding and leads to cell instability and degradation. To mitigate these effects, groups have investigated the creation of liquid specific pathways in the porous layers to alleviate liquid buildup and enhance gas diffusion. While some progress has been made, traditionally manufactured GDLs, which consist of randomly distributed carbon fibers, are limiting. 3D printed CAs are a promising solution as complex macroporous electrode structures can be manufactured out of micro and nano porous filaments with a high level of control. Additionally, the process may allow for the consolidation of multiple layers (MPL, GDL, & flow channels) into a single printed architecture. In this work various CA lattice structures were printed using a direct ink write (DIW) method and liquid breakthrough pressures were measured to demonstrate the ability to tune the water pathways to achieve specific pressure thresholds. Furthermore, a discussion of the prospects for printed CA electrodes in PEFC will focus on material properties, synthesis techniques, and current challenges.

36 MATERIALS SCIENCE↗

Milone eTape Liquid Level Sensor Laboratory Calibration with a Commercial 12.2 cm HS-Flume and 3D Printed 4 cm Micro-HS-Flumes

The NGEE Arctic Rainfall Simulator (NARS) is a variable intensity rainfall simulator (RFS) with a frame design based on the Humphry et al. (2002) RFS and a water delivery system based on the Walnut Gulch (Paige et al., 2004) RFS. The NARS uses an aluminum frame that is fully deconstructable for transportation to field locations and a water system that enables variable rain intensity. Prior to field deployment, H-flume discharge and the corresponding Milone eTape Liquid Level Sensor (eTape) resistance values were measured in the laboratory so that discharge measurements from the NGEE Arctic Rainfall Simulator could be automated. eTape resistance was measured with increasing fluid heights for the full range of the eTape to calculate sensor detection limits and resolution. The eTape was calibrated to both a commercially available 12.2 cm HS-flume and a 3D printed 4 cm Micro-HS-flume. This data package contains two .csv files, one for the eTape calibration and the other for the flume calibrations, and two .stl files to 3D print the 4 cm Micro-HS-Flume design with a 1 cm x 3.6 cm stilling well opening. The .stl files can be opened in most 3D printing or CAD programs/software. Two .kml files of the laboratory location and broader area where testing was conducted are also included in this data package.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Effect of rice husk ash-derived activator on the structural build-up of alkali activated materials

Highlights: • Filtered and unfiltered sodium silicate solutions were synthesised from RHA. • The dissolution efficiency of RHA in NaOH solution was 76.3%. • RHA-derived activator showed a structural build-up comparable to the commercial activator in AAM pastes. • The undissolved residues in the unfiltered RHA-derived activator increased the yield stress. • Comparable compressive strength and early age gel formation were observed from both commercial and RHA-derived solutions. Waste-derived sodium silicates (SSs) were synthesised from rice husk ash (RHA) to produce alkali activated materials (AAMs) using fly ash and slag as precursors. The effects of these SSs on the structural build-up were investigated by monitoring the evolution of the viscoelasticity, ultrasonic pulse waves, setting time, and infrared spectra. Two types of RHA derived SSs (filtered SS and unfiltered SS) were prepared to investigate the effect of the undissolved residue on the hardening process. The derived SS contained a large portion of monomer silicate species. The results showed that the structural build-up mechanism was comparable between the AAMs activated by the filtered SS and a commercial SS. The unfiltered SS increased the yield stress of the paste by up to 10 times. However, the residues in the unfiltered SS had insignificant impacts on the gel formation and compressive strength when using identical SiO{sub 2}/Na{sub 2}O and Na{sub 2}O/binder ratios in the mix design.

36 MATERIALS SCIENCE↗

Initial Results of the Geosynchronous Synthetic Thinned Array Radiometer (GeoSTAR)

An error budget is presented to meet 1 Kelvin radiometric accuracy in a geostationary atmospheric sounder with 50 km spatial resolution on the earth. The gain and phase errors are weighted by the magnitude of visibility versus antenna separation, and requirements range between approx.0.5% and 0.3 degrees of amplitude and phase, respectively, for the closest spacings at the center of the array, and about 5% and 3 degrees for the majority of the array. The latter requirement is met by our design without any special testing or stabilizations by reference signals. The former is met using an internal noise diode reference and by measuring the detailed antenna patterns on the antenna range. Biases and other additive errors in the raw visibility samples must be below about 2 mK on average, and this requirement is met by a phase shifting scheme applied to the local oscillator distribution. An outline of the data processing is presented, along with the first images from this system.

Synthetic Thinned Aperture Radiometer (STAR)↗

Continuous soil temperature measurements from 2019-10-4 to 2020-10-4, Teller road Mile 27, Seward Peninsula, Alaska

The dataset contains depth-resolved soil temperature measured at 45 discrete locations in a watershed located along the Nome-Teller road at Mile 27 in Seward Peninsula, Alaska. The dataset was generated to understand the local heterogeneity of soil thermal dynamics and their controls in a discontinuous permafrost region. At each location, temperatures were measured by a distributed temperature profiling probe designed based on Dafflon et al (2022). The dataset includes a description of the probe locations in the "Probe_locations.csv" file and the 45 data files (Soil_temperatures_*.csv). Metadata files include data descriptions (_dd.csv) for tabular data. All included files are listed and described in NGA513_flmd.csv.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Synthesis of nanograined zirconium diboride microsphere powder feedstock via emulsification of suspensions

Ceramic nanograined materials have desirable characteristics compared to their macroparticle counterparts but are rarely used in industrial applications due to issues with poor handleability and health hazards. Due to interparticle forces that become more dominant as the particle size decreases, it is difficult to use nanomaterials to fill dies, spread on surfaces, or flow through hoppers found in various manufacturing processes. In this work, we report a scalable gelcasting solution and unique emulsification process to create microspheres composed of nanoscale powders to enhance the flowability and handleability of nanomaterials. The gelcasting solution and emulsification process can be used with any nanoparticle composition that can be suspended in a liquid phase. This paper reports the effects of various parameters on zirconium diboride microsphere formation, such as surfactant content and mixing conditions. The microspheres maintain the nano-scale characteristics of the powder but improve its flowability by using cross-linked polyvinyl alcohol to combine irregularly shaped zirconium diboride nanoparticles with a particle diameter of 60 nm into larger spherical particles with a d 50 ~25 μm. This hierarchical feedstock engineering design combine the positive characteristics of materials across both length scales and improve the flowability of the feedstock from a Hausner Ratio of 1.56 to 1.19. The materials produced using this technique can be used in thermal plasma spray, die filling for hot pressing or spark plasma sintering, and binder jet printing applications.

36 MATERIALS SCIENCE↗

An Integrated Computer-Aided Design and Manufacturing Workflow for Synthetic Biology

Biological computer-aided design and manufacturing (bioCAD/CAM) tools facilitate the design and build processes of engineering biological systems using iterative design-build-test-learn (DBTL) cycles. In this book chapter, we highlight some of the bioCAD/CAM tools developed and used at the US Department of Energy (DOE) Joint Genome Institute (JGI), Joint BioEnergy Institute (JBEI), and Agile BioFoundry (ABF). We demonstrate the use of these bioCAD/CAM tools on a common workflow for designing and building a multigene pathway in a hierarchical fashion. Additionally, each tool presented in this book chapter is specifically tailored to support one or more specific steps in a workflow, can be integrated with the others into design and build workflows, and can be deployed at academic, government, or commercial entities.

59 BASIC BIOLOGICAL SCIENCES↗

Spontaneous assembly of hierarchical phases

We report the grand promise of self-assembly is the creation of target nanostructures through spontaneous molecular organization, a process that is — in principle — simpler and more scalable than laborious top-down nanofabrication methods. Yet self-assembly faces a fundamental challenge: the structures that form thermodynamically tend to minimize surface area and maximize symmetry; the most readily-accessible structures are thus quite simple. Block copolymer (BCP) self-assembly, for example, takes advantage of the chemical incompatibility along a polymer backbone to drive local phase separation; frustrated assembly leads to a nanoscale morphology whose unit cell is dictated by chain architecture. Canonical BCPs (linear chains with two blocks) form alternating lamellae and hexagonally-packed cylinders in a straightforward manner; but more exotic phases require additional control, for example directing the assembly using external forces, such as shear or chemical templates. An elegant alternative is to use synthetic methods to design more sophisticated chain architectures, which may give rise to new morphologies. An outstanding challenge is to achieve morphological control without undue synthetic burden. Sun et al. now report in Nature Nanotechnology the design and synthesis of novel triblock copolymers that give rise to structural order at multiple length scales, thereby forming complex and hierarchical nanoscale phases.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Experimental Calibration of Flow Rule Coefficients for LS-Dyna Mat_213

Composite materials have become a popular choice in aerospace engineering applications due to their low weight, high specific stiffness, high specific energy absorption, and economic synthesis. As use of composite materials has proliferated, the need for accurate simulation under extreme loading conditions is of increasing importance. *MAT_213 is a tabulated plasticity and damage material model in LS-DYNA designed for such use cases. To account for the nonlinear material response, a plasticity algorithm is used, which employs a non-associative flow rule with coefficients requiring experimental calibration. This work outlines an experimental methodology for calibrating these coefficients using the macroscopic stress-strain response and microscopic in-plane strain measurements from coupon scale experiments. The model material used for the development and demonstration of this methodology is a plain weave woven fabric with T300 carbon fiber tows in the warp direction and Kevlar© 49 fiber tows in the weft direction, and an Epon© 828/Epikure© 3223 thermoset epoxy matrix. Coupon-scale tensile testing performed at multiple fiber angles (carbon fibers oriented 0º, 22.5º, 45º, 67.5º, and 90º relative to the loading axis) provides data for multiple calibration processes. The measured plastic strain increments in the principal material coordinate are used to set limits for ratios between flow rule coefficients. The identified ranges are used to bound the search for a set of coefficients, leading to convergence of different coupon responses in the effective stress – effective plastic strain space. Flow rule coefficients found by this methodology are then used as (i) input for LS-DYNA simulations of uniaxial tension coupon tests at varying fiber angles, and (ii) comparison of predicted values for the plastic Poisson’s ratio in global coordinates with the experimentally measured one for all off-axis orientations. These results are quantitatively and qualitatively compared to macroscopic stress-strain curves and experimental strain components. The conformity of the experimentally measured quantities with those derived from the simulations provide a means for assessing the quality of calibrated coefficients.

Polymer Matrix Composites↗

Accelerating Biomimetic Solar - Energy Harvesting: Mapping the Interaction Landscape of Plasmonic-Excitonic Hybrid Nanosystems (Final Report)

In general, excitonic and plasmonic nanoscale materials in close proximity show high potential for significant breakthroughs in energy related materials research. The interactions between these two kinds of materials result in coupled optical transitions (plexcitons), distinct from those of both the individual exciton and plasmon as well as from those of the sum of their constituents (synergistic effects). By linking together materials-research and physical-research approaches, this project contributes to a concerted approach on nanomaterials energy research. The project’s overall goal is to accelerate the development of well-defined plexcitonic model systems consisting of carefully engineered plasmonic and excitonic nanomaterial— essential for both gaining a fundamental understanding of plexcitonic nanomaterials and the development of novel design principles for biomimetic solar energy harvesting. During the 3-year project period and the terminal renewal with limited support for a 12-month period, we successfully synthesized and characterized (1) a robust excitonic nanomaterial and (2) a library of plasmonic nanoparticles as well as developed (3) a microfluidic platform for homogenous nanosynthesis as summarized below: (1) Robust Excitonic Nanomaterial. Supramolecular assemblies are Nature’s most successful material system for solar energy harvesting. However, photovoltaic devices based on artificial supramolecular assemblies continue to be stymied by disappointing efficiencies and poor stability. The conceptual failure may lie in current solar cell architectures, which rely on solidifying supramolecular assemblies as an ensemble into a solid matrix, neglecting the intrinsic fragility of the assemblies’ internal structure, thus disrupting or even destroying their delicate optoelectronic properties, that is, delicate Frenkel excitonic properties. Supramolecular assemblies may finally serve as usable light harvesting material systems for solar energy conversion technologies, only if they meet the following criteria: (a) Stability, that is, the fragile structure including its delicate Frenkel excitonic character needs to be stable, (b) Robustness, that is, resistant against elevated and fluctuating temperatures, and (c) Viability for device integration, that is, capable of being immobilized onto solid substrates. Here, by developing a nanocomposite via a tunable, cage-like scaffold design, we successfully provided stable supramolecular nanocomposites, that inhabit robust Frenkel excitons despite harming environmental conditions such as extreme heat stress. (2) Library of Plasmonic Nanoparticles. Naturally, current models describing plasmonic hybrid quantum states—plasmonic hybridizations—parallel those developed for molecular orbitals, equating individual plasmonic nanostructures with “atoms” and the plasmonic nanoassemblies with “molecules.” In analogy to organic synthesis, a suitably robust fabrication method would allow for “atom-like” manipulation of “molecule-like” plasmonic nanoassemblies; of high value for next-generation energy nanotechnologies. Despite this frequent comparison, current plasmonic nanoassembly fabrication methods favor top-down templating over wet-chemical synthesis, however, achieving precise control over nanostructure’s geometry and surface characteristics remain an art and a scientific challenge. The conceptual failure may lie in the current wet-chemical synthesis paradigm, as it relies on the accessibility of a multi-dimensional synthesis parameter space through limited, rather one-dimensional synthesis procedures by employing step-by-step approaches. Solution-based nanoarchitectonics for rational design of precisely built plasmonic nanoassemblies via solution-based fabrication may finally be possible only if multi-dimensional syntheses approaches are available that allow for comprehensive control over the plasmonic nanomaterials’ (a) Structural Properties and (b) Surface Properties. Here, by developing an innovative multidimensional 1,3-propanediol based polyol synthesis, we successfully provided control over the plasmonic building-block’s geometry (size and shape) together with its surface characteristics. Our results present a critical step toward the vision of a “periodic table-like” system for plasmonic materials based on straightforward wet-chemical syntheses for energy nanotechnologies. Developing deliberate modifications on this synthesis, we generated a library of plasmonic nanostructures covering the vast parameter space—opening the door for fundamental investigation of plexcitonic model systems. (3) Microfluidic Platform for Homogenous Nanosynthesis. Control over structural properties of plexcitonic nanocomposites remains a challenge due to current limitations in nanosynthesis techniques. Slight variations in nanostructure’s geometry impact their optoelectronic properties, demanding precise synthesis beyond the capabilities of solution-based (batch) synthesis processes. In contrast, the small, confined liquid volumes used in microfluidics—a reaction technique where the manipulation of fluids takes place in channels with dimensions of tens of micrometers—allows for homogenous synthesis conditions, providing excellent control of the reaction and, as a result, of the materials’ geopmetry and composition. However, thus far, the majority of plexcitonic systems has been developed via batch synthesis. Here, by successfully developing a two-channel microreactor, our microfluidic-supported synthesis approach combines the advantages of both microfluidics and batch platforms, allowing for precise spatio-temporal control over all synthesis parameters opening the possibility for homogenous nanosythnesis of well-defined plexcitonic model systems.

14 SOLAR ENERGY↗