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Dimetalloylene (M‐E‐M) Complexes of Heavier Main Group Elements Ge, Sn, Pb, Bi via Cleavage of E‐X Bonds (X=N(SiMe 3 ) 2 , O t Bu) with an Iridium Hydride

Abstract Reactions of the Ir V hydride [ Me BDI Dipp ]IrH 4 {BDI=(Dipp)NC(Me)CH(Me)CN(Dipp); Dipp=2,6‐ i Pr 2 C 6 H 3 } with E[N(SiMe 3 ) 2 ] 2 (E=Sn, Pb) afforded the unusual dimeric dimetallotetrylenes ([ Me BDI Dipp ]IrH) 2 ( μ 2 ‐E) 2 in good yields. Moreover, ([ Me BDI Dipp ]IrH) 2 ( μ 2 ‐Ge) 2 was formed in situ from thermal decomposition of [ Me BDI Dipp ]Ir(H) 2 Ge[N(SiMe 3 ) 2 ] 2 . These reactions are accompanied by liberation of HN(SiMe 3 ) 2 and H 2 through the apparent cleavage of an E−N(SiMe 3 ) 2 bond by Ir−H. In a reversal of this process, ([ Me BDI Dipp ]IrH) 2 ( μ 2 ‐E) 2 reacted with excess H 2 to regenerate [ Me BDI Dipp ]IrH 4 . Varying the concentrations of reactants led to formation of the trimeric ([ Me BDI Dipp ]IrH 2 ) 3 ( μ 2 ‐E) 3 . The further scope of this synthetic route was investigated with group 15 amides, and ([ Me BDI Dipp ]IrH) 2 ( μ 2 ‐Bi) 2 was prepared by the reaction of [ Me BDI Dipp ]IrH 4 with Bi(NMe 2 ) 3 or Bi(O t Bu) 3 to afford the first example of a “naked” two‐coordinate Bi atom bound exclusively to transition metals. A viable mechanism that accounts for the formation of these products is proposed. Computational investigations of the Ir 2 E 2 (E=Sn, Pb) compounds characterized them as open‐shell singlets with confined nonbonding lone pairs at the E centers. In contrast, Ir 2 Bi 2 is characterized as having a closed‐shell singlet ground state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prospective Life Cycle Assessment of Synthetic Graphite Manufactured via Electrochemical Graphitization

Lithium-ion batteries (LIBs) are expected to play a crucial role in meeting many of the clean energy-related goals. Due to its electrical properties such as good conductance, chemical inertness, and corrosion resistance, graphite is a very popular anode for LIBs. Traditional methods of producing battery-grade graphite (high purity >99%) include processing naturally mined graphite or manufacturing synthetic graphite via the Acheson process, which converts soft amorphous carbons such as petroleum coke into graphite by subjecting it to high temperature (up to 3000 °C) for prolonged periods of times (3–5 days). However, due to a lack of abundant high purity natural graphite sources, synthetic graphite is the preferred choice for many LIBs. A new synthetic electrochemical graphitization method that subjects the amorphous carbon precursor submerged in a molten salt mixture to a constant cathodic polarization (against a graphitic anode) has been discovered that has significantly lower graphitization temperatures (~800 °C) and reduced graphitization time (3–6 h). Furthermore, the method can accept a higher variety of carbon precursors compared to the Acheson process. A prospective life cycle assessment (LCA) is conducted on this new method and compared against the traditional processes. The laboratory-scale demonstration of the method is used to build an inventory, which through various assumptions is scaled up to a commercial scale. An additional scenario is also considered with a biomass-derived carbon precursor for the graphite. The results from the LCA show that while the laboratory scale process is similar to the Acheson process and natural flake graphite in terms of impact, the scaled-up process is drastically better than the Acheson process in all environmental categories. Using a coconut shell-derived biomass precursor has a higher impact due to its manufacturing in Indonesia, as the Indonesian energy grid is highly fossil fuel dependent. Therefore, the biomass carbon may have a higher impact than petroleum coke dependent on the location of production of biomass-derived carbon black. The LCA has identified the molten salt—CaCl 2 —as a potential hotspot and suggests other salts should be considered. Accordingly, the new method shows promise in this early stage LCA in improving the environmental performance of graphite (and by relation LIBs) and therefore needs to be explored more in terms of its commercial viability.

25 ENERGY STORAGE↗

A rigorous physics-based enhanced parameter estimation (EPE) methodology for calibration of building energy simulations

Buildings rarely perform as designed/simulated and there are numerous tangible benefits if this gap is reconciled. A new scientifically rigorous yet pragmatic methodology for calibrating building energy simulations - called Enhanced Parameter Estimation (EPE) - is proposed that allows physically relevant parameter estimation rather than a blind force-fit to energy use data. Starting with a rapidly created simulation model, calibration is performed in two stages: (a) building shell calibration with the HVAC system replaced by an ideal system that meets the loads (b) HVAC system calibration with the building shell and all internal loads replaced by a box with only process loads. In the first stage, EPE identifies a small number of high-level heat flows in the energy balance, calculates them with specifically tailored individual driving functions, introduces physically significant parameters to best accomplish energy balance, and, estimates the parameters and their uncertainty bounds. Calibration is thus done with corrective heat flows without any arbitrary tuning of input parameters. Calibration accuracy is enhanced by machine learning of the residual errors. The EPE methodology is demonstrated by means of: a synthetic building and an actual 75,000 sq. ft. building in Pennsylvania. Future work needed for widespread application is discussed.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Control over Conformational Landscapes of Polypeptoids by Monomer Sequence Patterning

The ability to program chain conformation and structure through control over the monomer sequence of synthetic polymers has broad implications for next-generation material design. While related problems of protein-folding and de novo design have generated accurate predictions of 3D folded chain structures, generalization to synthetic polymers remains intractable due to the requirement of large structural databases and the intrinsically disordered nature of polymer building blocks. In this work, polypeptoids, a class of peptidomimetic synthetic polymers, are utilized to build a general workflow for the study of relationships between monomer sequence and dynamic 3D chain structure in solution. Furthermore, this work demonstrates how control over the monomer sequence can alter the conformational landscape of synthetic polymers to deviate dramatically from classical chain statistics. Specifically, the distribution of end-to-end distances, as measured by double electron-electron resonance spectroscopy in dilute solvent, is systematically skewed towards shorter distances with an increasing number of hydrophobes and further refined by hydrophobe arrangement in amphiphilic polypeptoid chains.

36 MATERIALS SCIENCE↗

Correlating structural changes in thermoresponsive hydrogels to the optical response of embedded plasmonic nanoparticles

Stimuli-responsive microgels, composed of small beads with soft, deformable polymer networks swollen through a combination of synthetic control over the polymer and its interaction with water, form a versatile platform for development of multifunctional and biocompatible sensors. The interfacial structural variation of such materials at a nanometer length scale is essential to their function, but not yet fully comprehended. Here, we take advantage of the plasmonic response of a gold nanorod embedded in a thermoresponsive microgel (AuNR@PNIPMAm) to monitor structural changes in the hydrogel directly near the nanorod surface. By direct comparison of the plasmon response against measurements of the hydrogel structure from dynamic light scattering and nuclear magnetic resonance, we find that the microgel shell of batch-polymerized AuNR@PNIPMAm exhibits a heterogeneous volume phase transition reflected by different onset temperatures for changes in the hydrodyanmic radius (R H ) and plasmon resonance, respectively. The new approach of contrasting plasmonic response (a measure of local surface hydrogel structure) with R H and relaxation times paves a new path to gain valuable insight for the design of plasmonic sensors based on stimuli-responsive hydrogels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preparation of Macroscopic Low-Density Gold Foams with Good Machinability

Uniform, macroscopic monoliths (ranging from a few millimeters to a centimeter) of low-density gold foams with ~95% porosity and ~10-μm-diameter pores were prepared by the casting of gold-coated polystyrene core-shell particles followed by the thermal removal of the polymer core. The Au foams were composed of unique hollow gold spheres and showed superior mechanical integrity and resilience compared to the foams we previously reported. Highly efficient seeding and electroless gold-plating methods in this study caused a significant morphological transition in the gold coatings from coarse particles to fine particles, and finally, to a continuous layer. A modified, scalable casting approach to form large uniform monoliths (up to ~1-cm diameter) and a gentle baking condition to minimize undesirable densification of the final foams enabled us to develop a simple, efficient synthetic route to nanostructured macroscopic low-density gold foams. To demonstrate the improved mechanical stability and machinability, a representative monolithic Au foam (~0.9 g/cm 3 ) was carefully cut into the hollow cylinder of gold foams by a series of machining and processing steps. Finally, we tried to understand the unique mechanical behaviors and properties of this gold foam by nanoindentation measurement.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

How do supernova remnants cool? – I. Morphology, optical emission lines, and shocks

ABSTRACT Supernovae (SNe) inject ∼1051 erg in the interstellar medium, thereby shocking and heating the gas. A substantial fraction of this energy is later lost via radiative cooling. We present a post-processing module for the flash code to calculate the cooling radiation from shock-heated gas using collisional excitation data from mappings v. When applying this tool to a simulated SN remnant (SNR), we find that most energy is emitted in the EUV. However, optical emission lines ([O iii], [N ii], [S ii], H α, H β) are usually best observable. Our shock detection scheme shows that [S ii] and [N ii] emissions arise from the thin shell surrounding the SNR, while [O iii], H $\rm \alpha$, and H $\rm \beta$ originate from the volume-filling hot gas inside the SNR bubble. We find that the optical emission lines are affected by the SNR’s complex structure and its projection on to the plane of the sky because the escaping line luminosity can be reduced by 10–80 per cent due to absorption along the line of sight. Additionally, the subtraction of contaminating background radiation is required for the correct classification of an SNR on the oxygen or sulphur BPT diagrams. The electron temperature and density obtained from our synthetic observations match well with the simulation but are very sensitive to the assumed metallicity.

Astronomy & Astrophysics↗

2D kinetic-ion simulations of inverted corona fusion targets

Laser-driven “inverted corona” fusion targets have attracted interest as a low-convergence neutron source and platform for studying kinetic physics. The scheme consists of a hollow or gas-filled spherical shell made of deuterated plastic. The shell has one or more laser entrance holes (LEH), resembling a spherical hohlraum. The laser passes through the LEH’s and illuminates the interior surface of the shell, ablating a plasma that travels inward towards the target center. Long ion mean free paths in the converging plasma can lead to significant interpenetration, atomic mix, and other kinetic effects. Here, in this work we report on numerical simulations of inverted corona targets using the kinetic-ion, fluid–electron hybrid particle-in-cell (PIC) approach in 2D RZ geometry. 2D simulations suggest that shape effects do not have a significant impact on plasma evolution and observed yield trends are primarily the result of 1D kinetic mix mechanisms. Simulations are also compared against available experimental data recorded at the OMEGA laser facility. In particular, synthetic x-ray emission images show good qualitative agreement with experimental results, albeit with an apparent timing discrepancy for the two-sided vacuum target. More generally, we demonstrate the potential of hybrid-PIC simulations for full-system modeling and experimental design, including collisional absorption of laser energy, plasma evolution, mix, and fusion burn.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Local Electric Field Effects on Water Dissociation in Bipolar Membranes Studied Using Core–Shell Catalysts

The local electric field strength is thought to affect the rate of water dissociation (WD) in bipolar membranes (BPMs) at the catalyst–nanoparticle surfaces. Here, we study core–shell nanoparticles, where the core is metallic, semiconducting, or insulating, to understand this effect. The nanoparticle cores were coated with a WD catalyst layer (TiO2 or HfO2) via atomic layer deposition (ALD), and the morphology was imaged with transmission electron microscopy. Irrespective of the core material, these core–shell catalysts displayed comparable WD overpotentials at optimal mass loading, despite the hypothesized differences in the electric field strength across the catalyst particle suggested by continuum electrostatic simulations. Substantial atomic interdiffusion between the core and shell was ruled out by X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and diffuse reflectance optical measurements. However, the optimal mass loading of catalyst was roughly 1 order of magnitude higher for the conductive and high dielectric core materials than for the low dielectric insulating cores. These findings are consistent with the hypothesis that electric field screening within the core material focuses the electric field drop between particles such that larger film thicknesses can be tolerated. Collectively, these data support the idea that it is the local electric field at the molecular level that controls proton-transfer rates and that the metal core/dielectric-shell constructs introduced here modulate that field. Further materials and synthetic design may enable optimization of the electric field strength across the proton-transfer trajectory at the material surface.

Sarma, Prasad V↗

Anomalous thermal transport in Eshelby twisted van der Waals nanowires

Dislocations in van der Waals (vdW) layered nanomaterials induce strain and structural changes that substantially impact thermal transport. Understanding these effects could enable the manipulation of dislocations for improved thermoelectric and optoelectronic applications, but experimental insights remain limited. Here, in this study, we use synthetic Eshelby twisted vdW GeS nanowires (NWs) with single screw dislocations as a model system to explore the interplay between dislocation-induced structural modifications and lattice thermal conductivity. Our measurements reveal a monoclinic structure stabilized by the dislocation, leading to a substantial drop in thermal conductivity for larger-diameter NWs (70% at room temperature), supported by first-principles calculations. Interestingly, we also find an anomalous enhancement of thermal conductivity with decreasing diameter in twisted NWs, contrary to typical trends in non-twisted GeS NWs. This is attributed to increased conductivity near the NW cores due to compressive strain around the central dislocations, and aligns with a density-functional-theory-informed core–shell model. Our results highlight the critical role of dislocations in thermal conduction, providing fundamental insights for defect and strain engineering in advanced thermal applications.

36 MATERIALS SCIENCE↗

Synthesis of monodisperse high entropy alloy nanocatalysts from core@shell nanoparticles

We report that high-entropy alloy (HEA) nanoparticles (NPs) hold great promise in electrocatalysis because of their nearly unlimited compositions, tailorable active sites, and high durability. However, the synthesis of these compositionally complex structures as monodisperse NPs remains a challenge by colloidal routes because the different rates of metal precursor reduction lead to phase separation. Here, we report the conversion of core@shell NPs into HEA NPs through annealing, with conservation of sample monodispersity. This potentially general route for high-quality HEA NPs was demonstrated by preparing PdCu@PtNiCo NPs via seed-mediated co-reduction, wherein Pt, Ni, and Co were co-deposited on PdCu seeds in solution. These multimetallic NPs were then converted to single-crystalline and single-phase PdCuPtNiCo NPs through annealing. On account of their small particle size, highly dispersed Pt/Pd content, and low elemental diffusivity, these HEA NPs were found to be a highly efficient and durable catalyst for the oxygen reduction reaction. They were also highly selective for the four-electron transfer pathway. We expect that this new synthetic strategy will facilitate the synthesis of new HEA NPs for catalysis and other applications.

36 MATERIALS SCIENCE↗

Binding of carboxylate and water to monovalent cations

The interactions of carboxylate anions with water and cations are important for a wide variety of systems, both biological and synthetic. Here, in order to gain insight on properties of the local complexes, we apply density functional theory, to treat the complex electrostatic interactions, and investigate mixtures with varied numbers of carboxylate anions (acetate) and waters binding to monovalent cations, Li + , Na + and K + . The optimal structure with overall lowest free energy contains two acetates and two waters such that the cation is four-fold coordinated, similar to structures found earlier for pure water or pure carboxylate ligands. More generally, the complexes with two acetates have the lowest free energy. In transitioning from the overall optimal state, exchanging an acetate for water has a lower free energy barrier than exchanging water for an acetate. In most cases, the carboxylates are monodentate and in the first solvation shell. As water is added to the system, hydrogen bonding between waters and carboxylate O atoms further stabilizes monodentate structures. These structures, which have strong electrostatic interactions that involve hydrogen bonds of varying strength, are significantly polarized, with ChelpG partial charges that vary substantially as the bonding geometry varies. Overall, these results emphasize the increasing importance of water as a component of binding sites as the number of ligands increases, thus affecting the preferential solvation of specific metal ions and clarifying Hofmeister effects. Finally, structural analysis correlated with free energy analysis supports the idea that binding to more than the preferred number of carboxylates under architectural constraints are a key to ion transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observations of the Bright Star in the Globular Cluster 47 Tucanae (NGC 104)

The Bright Star in the globular cluster 47 Tucanae (NGC 104) is a post-asymptotic giant branch (post-AGB) star of spectral type B8 III. The ultraviolet spectra of late-B stars exhibit myriad absorption features, many due to species unobservable from the ground. The Bright Star thus represents a unique window into the chemistry of 47 Tuc. We have analyzed observations obtained with the Far Ultraviolet Spectroscopic Explorer, the Cosmic Origins Spectrograph aboard the Hubble Space Telescope, and the Magellan Inamori Kyocera Echelle Spectrograph on the Magellan Telescope. By fitting these data with synthetic spectra, we determine various stellar parameters (T {sub eff} = 10,850 ± 250 K, logg=2.20±0.13) and the photospheric abundances of 26 elements, including Ne, P, Cl, Ga, Pd, In, Sn, Hg, and Pb, which have not previously been published for this cluster. Abundances of intermediate-mass elements (Mg through Ga) generally scale with Fe, while the heaviest elements (Pd through Pb) have roughly solar abundances. Its low C/O ratio indicates that the star did not undergo third dredge-up and suggests that its heavy elements were made by a previous generation of stars. If so, this pattern should be present throughout the cluster, not just in this star. Stellar-evolution models suggest that the Bright Star is powered by a He-burning shell, having left the AGB during or immediately after a thermal pulse. Its mass (0.54 ± 0.16M {sub ⊙}) implies that single stars in 47 Tuc lose 0.1–0.2 M {sub ⊙} on the AGB, only slightly less than they lose on the red giant branch.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Unconventional Dark Radical Chemistry in Dense Molecular Clouds: Directed Gas-Phase Formation of Naphthyl Radicals

The synthetic pathways to aromatic molecules inside photon-shielded dense molecular clouds remain a fundamental, unsolved enigma in astrochemistry and astrophysics, with low-temperature molecular growth routes involving aromatic radicals, such as prototype bicyclic naphthyl (C 10 H 7 • ), implicated as key sources. Here, exploiting crossed molecular beam experiments augmented by electronic structure calculations, unexpected pathways are exposed leading to the gas-phase formation of 1- and 2-naphthyl via barrierless bimolecular reactions of atomic carbon (C) with indene (C 9 H 8 ) and of dicarbon (C 2 ) with styrene (C 8 H 8 ) accompanied by ring expansion and cyclization together with aromatization. These facile routes challenge conventional wisdom that aromatic radicals are formed in deep space solely via “bright” gas-phase photochemistry of their closed-shell polycyclic aromatic hydrocarbon (PAH) precursors. A hitherto disregarded “dark” aromatic radical chemistry with aromatic radicals synthesized via gas-phase reactions offers new concepts on the chemical evolution of the chemistry of dark molecular clouds eventually culminating in the rapid formation of aromatics, fullerenes, and carbonaceous nanostructures.

Aromatic compounds↗

Pilot Testing of a Highly Efficient Pre-combustion Sorbent-based Carbon Capture System

TDA developed and demonstrated a highly efficient pre-combustion carbon capture system. The overall objective of this work was to develop a new sorbent-based pre-combustion carbon capture technology for Integrated Gasification Combined Cycle (IGCC) power plants. In this project our goal was to demonstrate the techno-economic viability of the new technology by 1) demonstrating it in large-scale slipstream tests, and 2) carrying out a high fidelity engineering and cost analysis. TDA’s process used an advanced physical adsorbent that selectively removes CO 2 from coal-derived synthesis gas above the dew point of the gas at temperatures as high as 300°C. The sorbent consists of a mesoporous carbon whose surface was grafted with functional groups that remove CO 2 via a well-known acid-base interaction. As documented in bench-scale experiments and field tests with actual coal gas, the sorbent achieved a very high capacity for CO 2 at temperatures as high as 300°C. The sorbent bound CO 2 more strongly than common physical adsorbents, providing the chemical potential needed for the high temperature operation. However, because CO 2 does not form a true covalent bond with the surface sites (as is the case with chemical absorbents), the sorbent regeneration could be carried out with only a very small energy input. The heat input to regenerate our sorbent was only 4.9 kcal per mol of CO 2 , which is much lower than that for chemical absorbents (e.g., 29.9 kcal/mol CO 2 for sodium carbonate) and was similar to the requirements of physical solvents (e.g., 4 kcal/mol CO 2 for Selexol TM ). Because the sorbent operates above the dew point of the synthesis gas (unlike the Selexol TM process), a higher power cycle efficiency can be achieved. With previous DOE/NETL funding (Contract No. DE-FE-0000469), we demonstrated the techno-economic viability of the technology in bench-scale tests and slipstream demonstrations at the National Carbon Capture Center (NCCC), Wilsonville, Alabama and Wabash River IGCC plant in Terra Haute, Indiana. We demonstrated a stable working CO 2 capacity for over 11,650 cycles with simulated synthesis gas. We also evaluated its performance with actual synthesis gas in two test campaigns at the Wabash River IGCC Plant, Terre Haute, IN and the National Carbon Capture Center (NCCC), Wilsonville, AL. The slipstream tests clearly showed that the actual coal gas constituents and potential contaminants (e.g. trace metals, halides, tars) had no effect on the sorbent’s ability to remove CO 2 (the same sorbent beds were used in both field tests with no sign of deactivation for 2,000 cycles with over 26,750 SCF of gas treated). As expected, due to the high temperature CO 2 removal capability and low energy needed to regenerate the sorbent, the power cycle efficiency with our process was greater than 34% on a higher heating value (HHV) basis; in comparison, the same IGCC plant equipped with the Selexol TM solvent for carbon capture can only achieve 31.4% HHV efficiency. The capital cost for an IGCC system with TDA’s process is estimated as $2,417/kW e , which is 12% lower than that of the IGCC/ Selexol TM process. The levelized cost for electricity including the transport, storage and monitoring (TS&M) cost for CO 2 was calculated as $\$ $92.9/MWh (lowest reported to our knowledge), which is much better than the $105.2/MWh estimated for the IGCC/ Selexol TM process. In this project (DE-FE0013105), TDA Research, in collaboration with our partners Gas Technology Institute (GTI), Illinois Clean Coal Institute (ICCI), University of California, Irvine (UCI), University of Alberta (UOA), Siemens, NCCC and Sinopec advanced the technical maturity of the technology; scaling it up by a factor of 100. We optimized the reactor design using computational fluid dynamics (CFD); using adsorption modeling we improved the pressure swing adsorption (PSA) cycle sequence. We carried out two field test campaigns with a fully-equipped 0.1 MW e prototype unit (for a total of 844 hours) using actual synthesis gas to prove the viability of the new technology. A successful 30 day (707 hrs) evaluation was completed at NCCC under air blown gasification conditions. We demonstrated 97.3% carbon capture at 1,500 SLPM, 93% carbon capture at 1,800 SLPM, and 90% carbon capture at 2,100 SLPM in the NCCC tests. We also demonstrated the system for 137 hours at a Sinopec petrochemical plant under oxygen blown gasification, demonstrating 86% carbon capture at 2,660 SLPM. In collaboration with University of California, Irvine (UCI), we completed a techno-economic analysis (TEA) for TDA’s warm gas cleanup technology integrated to IGCC power plant. The net plant efficiencies (on a coal HHV basis) for the warm gas cleanup cases were estimated to be 34.0% for E-GasTM gasifier, 34.4% for GE gasifier, 33.4 for the Shell gasifier and 34.2 for the TRIG TM gasifier (Cases 2, 4, 6 and 8 in this study) with a catalytic combustor for CO 2 purification, which are significantly higher than those for the Cold Gas Case, or an increase of as much as 12% in the heat rate for Case 2, 6% for Case 4, 9% for Case 6, and 9% for Case 8. The 1st year cost of electricity with the transport, storage and monitoring (TS&M) costs for the CO 2 included was $\$ $129.2/MWh for the E-GasTM gasifier Warm Gas Cleanup Case, $\$ $131.9/MWh for the GE gasifier Warm Gas Cleanup Case, $\$ $146.8/MWh for the Shell Gasifier Warm Gas Cleanup Case, and $\$ $129.9/MWh for the TRIG TM gasifier Warm Gas Cleanup Case. For comparison, the costs for the baseline Cold Gas CO 2 removal with Selexol for the different gasifiers were: $\$ $146.6/MWh for the E-Gas TM gasifier, $\$ $142.2/MWh for the GE gasifier, $\$ $159.0/MWh for the Shell gasifier and $\$ $144.3/MWh for the TRIG TM gasifier. In summary, the costs for our system were 7 to 12% lower than the corresponding Cold Gas Cleanup cases. The results of this techno-economic analysis suggested that TDA’s high temperature PSA-based Warm Gas Clean-up Technology can make a substantial improvement in the IGCC plant thermal performance for achieving near zero CO 2 emissions for E-Gas TM , GE, Shell and TRIG TM gasifier based IGCC power plants. The capital expenses were estimated to be lower than that of Selexol’s™. Taken together, the higher net plant efficiency and lower capital and operating costs resulted in substantial reduction in the cost of carbon capture for the IGCC plant equipped with TDA’s high temperature PSA-based carbon capture system. Finally, in collaboration with Gas Technology Institute (GTI) we completed the environmental health and safety assessment for TDA’s warm gas carbon capture technology.

01 COAL, LIGNITE, AND PEAT↗

Synthesis and Characterization of a Bridging Cerium(IV) Nitride Complex

Complexes featuring lanthanide–ligand multiple bonds are rare and highly reactive. They are important synthetic targets to understand 4f/5d-bonding in comparison to d-block and actinide congeners. Herein, the isolation and characterization of a bridging cerium(IV)-nitride complex: [(TriNOx)Ce(Li 2 μ-N)Ce(TriNOx)][BAr F 4 ] is reported, the first example of a molecular cerium-nitride. The compound was isolated by deprotonating a monometallic cerium(IV)-ammonia complex: [Ce IV (NH 3 )(TriNOx)][BAr F 4 ]. The average Ce=N bond length of [(TriNOx)Ce(Li 2 μ-N)Ce(TriNOx)][BAr F 4 ] was 2.117(3) Å. Vibrational studies of the 15 N-isotopomer exhibited a shift of the Ce=N=Ce asymmetric stretch from ν = 644 cm –1 to 640 cm –1 , and X-ray spectroscopic studies confirm the +4 oxidation state of cerium. Furthermore, computational analyses showed strong involvement of the cerium 4f shell in bonding with overall 16% and 11% cerium weight in the σ- and π-bonds of the Ce=N=Ce fragment, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic Layers of B2 CuPd on Cu Nanocubes as Catalysts for Selective Hydrogenation

The search for highly active and selective catalysts with high precious metal atom utilization efficiency has attracted increasing interest in both the fundamental synthesis of materials and important industrial reactions. Here, in this work, we report the synthesis of Pd–Cu nanocubes with a Cu core and an ordered B2 intermetallic CuPd shell with controllable atomic layers on the surface (denoted as Cu/B2 CuPd), which can efficiently and robustly catalyze the selective hydrogenation of acetylene (C 2 H 2 ) to ethylene (C 2 H 4 ) under mild conditions. The optimized Cu/B2 CuPd with a Pd loading of 9.5 at. % exhibited outstanding performance in the C 2 H 2 semi-hydrogenation with 100% C 2 H 2 conversion and 95.2% C 2 H 4 selectivity at 90 °C. We attributed this outstanding performance to the core/shell structure with a high surface density of active Pd sites isolated by Cu in the B2 intermetallic matrix, representing a structural motif of single-atom alloys (SAAs) on the surface. The combined experimental and computational studies further revealed that the electronic states of Pd and Cu are modulated by SAAs from the synergistic effect between Pd and Cu, leading to enhanced performance compared with pristine Pd and Cu catalysts. This study provides a new synthetic methodology for making single-atom catalysts with high precious metal atom utilization efficiency, enabling simultaneous tuning of both geometric and electronic structures of Pd active sites for enhanced catalysis.

36 MATERIALS SCIENCE↗

Multilayered Ordered Protein Arrays Self-Assembled from a Mixed Population of Virus-like Particles

Biology shows many examples of spatially controlled assembly of cells and biomacromolecules into hierarchically organized structures, to which many of the complex biological functions are attributed. While such biological structures have inspired the design of synthetic materials, it is still a great challenge to control the spatial arrangement of individual building blocks when assembling multiple types of components into bulk materials. Here, in this study, we report self-assembly of multilayered, ordered protein arrays from mixed populations of virus-like particles (VLPs). We systematically tuned the magnitude of the surface charge of the VLPs via mutagenesis to prepare four different types of VLPs for mixing. A mixture of up to four types of VLPs selectively assembled into higher-order structures in the presence of oppositely charged dendrimers during a gradual lowering of the ionic strength of the solution. The assembly resulted in the formation of three-dimensional ordered VLP arrays with up to four distinct layers including a central core, with each layer comprising a single type of VLP. A coarse-grained computational model was developed and simulated using molecular dynamics to probe the formation of the multilayered, core-shell structure. Our findings establish a simple and versatile bottom-up strategy to synthesize multilayered, ordered materials by controlling the spatial arrangement of multiple types of nanoscale building blocks in a one-pot fabrication.

59 BASIC BIOLOGICAL SCIENCES↗