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At least 919 records · Page 51

Polyhalohydrins: Investigating Vicinal Functionalities by Ring-Opening of Epoxides on Polyolefins

Halohydrins are functional groups that are underexplored in polymer science. This study synthesized and examined structure–property relationships of halohydrin-functionalized polymers derived from polycyclooctene (PCOE), which was obtained via ring-opening metathesis polymerization (ROMP). The polyhalohydrins, including polychlorohydrin, polybromohydrin, and polyiodohydrin, were produced through a two-step process involving epoxidation of PCOE followed by epoxide ring-opening using hydrochloric, hydrobromic, or hydroiodic acid. These stereoirregular and regioirregular polymers are amorphous as measured by differential scanning calorimetry and X-ray scattering. Lap joint shear testing revealed an enhanced adhesive performance in polychlorohydrin and polybromohydrin, with the former demonstrating nearly three times the ultimate shear stress compared to a model polyethylene, hydrogenated PCOE. Additionally, contact angle measurements and surface free energy analysis showed an increase in hydrophilicity and polarity from iodine- to bromine- to chlorine-functionalized polyhalohydrins, aligning with trends in adhesion strength. Furthermore, these results underscore the potential of halohydrin functionalization as a versatile approach for tuning surface properties, offering new opportunities for polymer-to-polymer transformations.

Functional groups↗

Fractal Model for Drag Reduction on Multiscale Nonwetting Rough Surfaces

Rough surfaces in contact with a flow of fluid exhibit alternating no-slip and free shear boundary conditions at the solid–liquid and air–liquid interfaces, respectively, thereby potentially offering drag reduction benefits. The balance between the dynamic pressure in the flow and the restoring capillary pressure in the interasperity spaces determines the stability of the Cassie state of wettability and is a function of the relative extent of no-slip and free shear regions per unit surface area. In the present study, using a fractal representation of rough surface topography, an analytical model is developed to quantify the stability of the Cassie state of wettability as well as drag reduction and the friction factor for laminar flow in a rectangular channel between nonwetting multiscale rough surfaces. A systematic study is conducted to quantify the effects of fractal parameters of the surfaces and the flow Reynolds number on drag reduction and the friction factor. The studies are used to develop friction factor curves extending the classical Moody diagram to hydrophobic and superhydrophobic surfaces. On the basis of the studies, regime maps are derived for estimating the extent of drag reduction offered by hydrophobic and superhydrophobic surfaces, revealing that superhydrophobic surfaces do not always offer the best drag reduction performance. The application of the fractal model to practical topographies of nonwetting surfaces of copper, aluminum, and zinc oxide fabricated via electrodeposition and etching is also discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Constructing Highly Durable Fuel Cell Catalysts Through Integrating Graphitic Shell‐Protected Composite Carbon Support with Gaseous Co Deposition‐Driven PtCo Intermetallics

Metal dissolution, nanoparticle agglomeration, and carbon support corrosion cause significant performance degradation of current PtCo catalysts under acidic and oxidative oxygen reduction reaction. Here, in this study, an integrated strategy is presented to design high-performance Pt 3 Co intermetallic catalysts by regulating gaseous Co deposition-driven diffusion into Pt nanoparticles supported on a composite carbon. The composite carbon is derived from ZIF-8/polyaniline, consisting of a high-surface-area (HSC) core and a protective graphitic shell (GS), which is employed to design 40 wt.% Pt/HSC@GS catalyst. The corresponding membrane electrode assemblies (MEAs) can maintain 1.09 A cm −2 at 0.7 V (20. 7% loss) after 10 000 cycles (1.0–1.5 V for carbon stability) and 1.15 A cm −2 (16.1% loss) after 150 000 cycles (0.60–0.95 V for catalyst stability). A ordered Pt 3 Co intermetallic is synthesized via a gaseous Co-deposition process, which yields a homogeneous Co-rich layer onto the Pt nanoparticles on the composite support, thereby facilitating Co diffusion into Pt crystal during subsequent ordering annealing to form the ordered intermetallic structure. This gaseous deposition leads to a thin carbon layer on PtCo nanoparticles, inhibiting particle growth during the annealing and mitigating Co dissolution under dynamic electrochemical conditions. The PtCo catalyst achieves impressive MEA performance and long-term durability (1.45 A cm −2 at 0.7 V after 120 000 cycles) under heavy-duty conditions.

30 DIRECT ENERGY CONVERSION↗

Effect of grafting density on the two-dimensional assembly of nanoparticles

Employing grazing-incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that films composed of polyethylene glycol (PEG)-grafted silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs), as well as their binary mixtures, form highly stable hexagonal structures at the vapor–liquid interface. These nanoparticles exhibit remarkable stability under varying environmental conditions, including changes in pH, mixing concentration, and PEG chain length. Short-chain PEG grafting produces dense, well-ordered films, while longer chains produce more complex, less dense quasi-bilayer structures. AuNPs exhibit higher grafting densities than AgNPs, leading to more ordered in-plane arrangements. In binary mixtures, AuNPs dominate the population at the surface, while AgNPs integrate into the system, expanding the lattice without forming a distinct binary superstructure. In conclusion, these results offer valuable insights into the structural behavior of PEG-grafted nanoparticles and provide a foundation for optimizing binary nanoparticle assemblies for advanced nanotechnology applications.

36 MATERIALS SCIENCE↗

Innovative use of CaO in combination with amino acid salt to convert CO 2 as CaCO 3 nanoparticles under mild pH and low temperature

The increasing demand for sustainable CO 2 management has driven the development of innovative methods that can convert point source CO 2 into value-added products. In this study, CaO in combination with amino acid salt was used to convert CO 2 into CaCO 3 nanoparticles. Different from the conventional method where CO 2 diffusion presents a major challenge in reacting with CaO to form CaCO 3 , amino acid salt solvent was applied to absorb CO 2 first and then rapidly reacted with CaO to form CaCO 3 nanoparticles (∼50 nm) at a low temperature (e.g., 60 °C). Our experiments showed that at a glycine (Gly)/NaOH ratio of 2:1 or 3:1, the solution pH values during the CO 2 absorption and conversion were about 8–9 at 60 °C, while at a ratio of 1:1, the solution pH values were about 9–11; without Gly, the solution pH values were about 12. Gly-optimized solvent substantially reduced corrosion risk to reactors. In addition, the use of amino acid (i.e., Gly) led to much smaller CaCO 3 particles, distinctly different chemical phases, and fundamentally different chemical reactions. Moreover, in the presence of Gly, the solution pH was completely reversed and the solution was regenerated for cyclic use when CaO was added. The solvent was recyclable and reusable, highlighting the cost-effectiveness and sustainability of this approach. The Gly-modulated CaCO 3 nanoparticles may have significant potential for industrial applications in the biomedicine, construction, plastics, and rubber industries.

36 MATERIALS SCIENCE↗

Nucleon momentum fraction, helicity and transversity from 2+1-flavor lattice QCD

A detailed analysis of the systematic uncertainties in the calculation of the isovector momentum fraction, ( x ) u - d , helicity moment, ( x ) Δ u - Δ d , and the transversity moment, ( x ) δu - δd , of the nucleon is presented using high-statistics data on seven ensembles of gauge configurations generated by the JLab/W&M/LANL/MIT collaborations using 2 + 1-flavors of dynamical Wilson-clover quarks. The much higher statistics have facilitated better control over all systematics compared to previous lattice calculations. The least understood systematic — excited-state contamination — is quantified by studying the variation of the results as a function of different estimates of the mass gap of the first excited state, obtained from two- and three-point correlation functions, and as a function of the pion mass M π . The final results are obtained using a simultaneous fit in the lattice spacing a , pion mass M π and the finite volume parameter M π L keeping leading order corrections. The data show no significant dependence on the lattice spacing and some evidence for finite-volume corrections. Our final results, in the $ \overline{\mathrm{MS}} $ scheme at 2 GeV, are ( x ) u - d = 0 . 155(17)(20), ( x ) Δ u - Δ d = 0 . 183(14)(20) and ( x ) δu - δd = 0 . 220(18)(20), where the first error is the overall analysis uncertainty assuming excited-state contributions have been removed, and the second is an additional systematic uncertainty due to possible residual excited-state contributions. These results are consistent with phenomenological global fit values.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Emergence of topological and trivial interface states in VSe 2 films coupled to Bi 2 Se 3

Coupling ordinary metals with topological Bi 2 Se 3 can instigate the long-range migration of the spin-polarized Dirac states. Instead, for trivial metallic VSe 2 films on Bi 2 Se 3 , topological and trivial Rashba-type interface states emerge, each strongly localized at the VSe 2 /Bi 2 Se 3 interface. Their rapidly decaying spectral weights are uncovered by thickness-dependent band mappings of VSe 2 films and replicated by a phenomenological first-principles model of the spectral function. In this work, the results are pertinent to spintronic devices requiring spin transmission across metal/topological insulator interfaces.

36 MATERIALS SCIENCE↗

Single-Phase Spinel NiCo 2 O 4 as Highly Active and Stable Electrocatalysts for Urea Oxidation Reaction in Urea Electrolysis

Exploring and designing a stable and active catalyst for the urea electro-oxidation reaction (UOR, CO(NH 2 ) 2 + 6OH – → CO 2 + N 2 + 5H 2 O + 6e – ) is crucial for the long-term sustainability of ecological systems and clean energy production. We found that spinel NiCo 2 O 4 is a stable and active electrocatalyst for UOR at a relatively low anodic potential without triggering the competing oxygen evolution reaction (OER). A urea electrolysis cell (CO(NH 2 )2 + H 2 O → CO 2 + N 2 + 2H 2 ) utilizing a spinel NiCo 2 O 4 anode and a commercial Pt cathode was further characterized through galvanostatic polarization tests, demonstrating excellent structural stability at various current densities. Post-mortem analysis of long-term urea electrolysis measurements suggested that NiCo 2 O 4 electrocatalysts maintained a stable spinel structure. However, redistribution of Ni 3+ to Ni 2+ valence on the catalyst surface was observed, in contrast to the intact Co valence, indicating that (i) Ni sites are active toward urea adsorption and sequential electro-oxidation; (ii) while urea oxidation proceeds primarily through the direct electro-oxidation mechanism, chemical reactions between the Ni 3+ site and urea occur during long-term electrochemical UOR operation. Density functional theory (DFT) simulations were used to calculate the adsorption energies of urea molecules on NiO, Co 3 O 4 , and NiCo 2 O 4 , revealing the importance of regulating the configuration of adsorbed urea molecules on the NiCo 2 O 4 surface.

36 MATERIALS SCIENCE↗

Highly dense atomic Fe–Ni dual metal sites for efficient CO 2 to CO electrolyzers at industrial current densities

Carbon-supported, atomically dispersed, nitrogen-coordinated metal sites (e.g., Fe and Ni) are arguably the most promising catalysts for the electrochemical reduction of CO 2 to CO due to their unique catalytic properties and the use of earth-abundant elements. However, conventional single metal sites are constrained by their structural simplicity, causing either too weak or too strong absorption/desorption of multiple critical intermediates (e.g., *COOH and *CO). Current catalysts also suffer from ultra-low loadings (<1.0 wt%) of atomic metal active sites in catalysts, leading to inadequate performance for CO 2 -to-CO conversion. Here, we develop dual Ni/Fe metal site catalysts with significantly increased atomically dispersed metal loadings (up to 4.8 wt%). A gas-phase chemical vapor deposition (CVD) approach to introducing single Ni sites was integrated with Fe 2 O 3 /ZIF-8 precursors, followed by an optimal thermal activation. The optimized CVD-Ni/Fe–N–C catalyst exhibited remarkable electrocatalytic performance for the CO 2 reduction to CO in a continuous membrane-electrode-assembly electrolyzer, achieving a maximum CO faradaic efficiency (FE CO ) of 96% at a current density of 700 mA cm −2 in a near-neutral electrolyte. Furthermore, a desirable but challenging acidic flow-cell electrolyzer was designed using this dual metal site catalyst to improve CO 2 utilization, accomplishing a FE CO of up to 95% at a CO partial current density close to 600 mA cm −2 . Density functional theory (DFT) calculations suggest a synergetic effect between Fe–Ni pairs facilitating *COOH intermediate formation and *CO desorption simultaneously during CO 2 to CO conversion. This is key to breaking the linear scaling relationship of conventional single-metal site catalysts during the CO 2 reduction reaction.

36 MATERIALS SCIENCE↗

Fast inversion, preconditioned quantum linear system solvers, fast Green's-function computation, and fast evaluation of matrix functions

Preconditioning is the most widely used and effective way for treating ill-conditioned linear systems in the context of classical iterative linear system solvers. We introduce a quantum primitive called fast inversion, which can be used as a preconditioner for solving quantum linear systems. The key idea of fast inversion is to directly block encode a matrix inverse through a quantum circuit implementing the inversion of eigenvalues via classical arithmetics. We demonstrate the application of preconditioned linear system solvers for computing single-particle Green's functions of quantum many-body systems, which are widely used in quantum physics, chemistry, and materials science. We analyze the complexities in three scenarios: the Hubbard model, the quantum many-body Hamiltonian in the plane-wave-dual basis, and the Schwinger model. We also provide a method for performing Green's function calculation in second quantization within a fixed-particle manifold and note that this approach may be valuable for simulation more broadly. Aside from solving linear systems, fast inversion also allows us to develop fast algorithms for computing matrix functions, such as the efficient preparation of Gibbs states. Furthermore, we introduce two efficient approaches for such a task, based on the contour-integral formulation and the inverse transform, respectively.

97 MATHEMATICS AND COMPUTING↗

First-principles computations of the Stark shift of a defect-bound exciton: The case of the T center in silicon

The T center in silicon has recently drawn a lot of attention for its potential in quantum information science. The sensitivity of the zero-phonon line (ZPL) to electrical field was recently investigated by a combination of different experimental methods but there are still few first principles studies on the Stark shift of the T center. Dealing with the defect-bound exciton nature of the excited state is particularly challenging using density functional theory because of the large spatial delocalization associated with the wavefunction. Here, in this work, we tackle this issue by performing a convergence study over the supercell size. We obtain an exciton binding energy of 28.5 meV, in good agreement with experimental results. We then calculate the Stark shift through the dipole moment change of the ZPL transition of the T center using the modern theory of polarization formalism and find a modest linear coefficient of Δ⁢𝜇=0.79⁢D along X and Δ⁢𝜇=0.03⁢𝐷 along Y. We discuss our results in light of the recent experimental measurements of the Stark shift. Our analysis suggests that bound-exciton defects could be particularly sensitive to local field effect as a result of their large spatial extent.

color centers↗

From magnetic order to quantum disorder in the Zn-barlowite series of S = 1/2 kagomé antiferromagnets

We report a comprehensive muon spectroscopy study of the Zn-barlowite series of $S=\frac{1}{2}$ kagomé antiferromagnets, Zn x Cu 4-x (OH) 6 FBr, for x= 0.00 to 0.99(1). By combining muon spin relaxation and rotation measurements with state-of-the-art density-functional theory muon-site calculations, we observe the formation of both μ–F and μ–OH complexes in Zn-barlowite. From these stopping sites, implanted muon spins reveal the suppression of long-range magnetic order into a possible quantum spin liquid state upon the increasing concentration of Zn-substitution. In the parent compound (x = 0), static long-range magnetic order below T N = 5 K manifests itself in the form of spontaneous oscillations in the time-dependent muon asymmetry signal consistent with the dipolar fields expected from the calculated muon stopping sites and the previously determined magnetic structure of barlowite. Meanwhile, in the x = 1.0 end-member of the series—in which antiferromagnetic kagomé layers of Cu 2+ $S=\frac{1}{2}$ moments are decoupled by diamagnetic Zn 2+ ions—we observe that dynamic magnetic moment fluctuations persist down to at least 50 mK, indicative of a quantum disordered ground state. We demonstrate that this crossover from a static to dynamic magnetic ground state occurs for compositions of Zn-barlowite with x > 0.5, which bears resemblance to the dynamical behaviour of the widely studied Zn-paratacamite series that contains the quantum spin liquid candidate herbertsmithite.

36 MATERIALS SCIENCE↗

Microgrid Controller Survey Report: 2024 Update

In the past decade, the number of microgrids deployed by electric utilities, end-use customers, and third parties has been increasing significantly both in the US and worldwide. The increase is driven by various reasons, such as carbon emission reduction, energy efficiency improvement, reliability and resilience enhancement, energy infrastructure modernization, and more. Microgrid controllers, as the most important components in these deployed microgrids, optimally coordinate the operation and control of the microgrid assets (e.g., distributed energy resources [DERs], energy storage systems, demand response, and even electric vehicles) and ensure that the microgrid is being operated in an efficient, clean, and resilient manner. To that end, the market for microgrid controllers has been growing rapidly in recent years. Various microgrid controllers have been released and continuously updated by vendors to satisfy the different needs of microgrid customers. However, the functionalities demonstrated by microgrid controllers released by different vendors show a huge difference because of a lack of widely known and accepted industrial standards, and various microgrid customers have specific requirements for different applications and scenarios. To obtain a clear view of the current state of the commercial microgrid controllers’ functionalities and identify potential research gaps, a survey of the functionalities of commercial microgrid controllers and the Advanced Distribution Management System (ADMS) developed by vendors and national laboratories was conducted in 2023. The results of the survey are presented in this report with the current status of commercial microgrid controllers analyzed, potential research gaps identified, and future research trends revealed.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Valence-free open nanoparticle superlattices

A cornerstone of advanced materials design is establishing a framework for assembling nanoparticle superstructures with tailored symmetries. A longstanding challenge has been assembling diamond-like superstructures for photonic devices. Traditionally, such open superstructures require functionalized nanoparticles with directional or anisotropic interactions, reminiscent of valence bonding in a diamond. Here, we present a robust strategy for assembling valence-free nanoparticles into a broad array of cubic superstructures. By grafting nanoparticles with oppositely charged, end-functionalized water-soluble polymers of adjustable molecular weight, we gain control over electrostatic interactions and conformational constraints. This unified approach yields lattices analogous to rock salt, CsCl, zinc-blende, diamond, and the rare simple cubic phase, with tunable lattice constants. Theoretical models and simulations elucidate the underlying interactions, providing a framework for engineering valence-free nanoparticle superlattices.

36 MATERIALS SCIENCE↗

Investigation into the event-activity dependence of $\Upsilon$(nS) relative production in proton-proton collisions at $ \sqrt{s} $ = 7 TeV

The ratios of the production cross sections between the excited ϒ(2S) and ϒ(3S) mesons and the ϒ(1S) ground state, detected via their decay into two muons, are studied as a function of the number of charged particles in the event. The data are from proton-proton collisions at $ \sqrt{s} $ = 7 TeV, corresponding to an integrated luminosity of 4.8 fb$^{−1}$, collected with the CMS detector at the LHC. Evidence of a decrease in these ratios as a function of the particle multiplicity is observed, more pronounced at low transverse momentum $ {p}_{\mathrm{T}}^{\upmu \upmu} $. For ϒ(nS) mesons with $ {p}_{\mathrm{T}}^{\upmu \upmu} $> 7 GeV, where most of the data were collected, the correlation with multiplicity is studied as a function of the underlying event transverse sphericity and the number of particles in a cone around the ϒ(nS) direction. The ratios are found to be multiplicity independent for jet-like events. The mean $ {p}_{\mathrm{T}}^{\upmu \upmu} $ values for the ϒ(nS) states as a function of particle multiplicity are also measured and found to grow more steeply as their mass increases.[graphic not available: see fulltext]

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Electronic structure of mononuclear Cu-based molecule from density-functional theory with self-interaction correction

In this paper, we investigate the electronic structure of a planar mononuclear Cu-based molecule [Cu(C 6 H 4 S 2 ) 2 ] z in two oxidation states ( z = –2, –1) using density-functional theory (DFT) with Fermi–Löwdin orbital (FLO) self-interaction correction (SIC). The dianionic Cu-based molecule was proposed to be a promising qubit candidate. Self-interaction error within approximate DFT functionals renders severe delocalization of electron and spin densities arising from 3 d orbitals. The FLO-SIC method relies on optimization of Fermi–Löwdin orbital descriptors (FODs) with which localized occupied orbitals are constructed to create SIC potentials. Starting with many initial sets of FODs, we employ a frozen-density loop algorithm within the FLO-SIC method to study the Cu-based molecule. We find that the electronic structure of the molecule remains unchanged despite somewhat different final FOD configurations. In the dianionic state (spin S = 1/2), FLO-SIC spin density originates from the Cu d and S p orbitals with an approximate ratio of 2:1, in quantitative agreement with multireference calculations, while in the case of SIC-free DFT, the orbital ratio is reversed. Overall, FLO-SIC lowers the energies of the occupied orbitals and, in particular, the 3 d orbitals unhybridized with the ligands significantly, which substantially increases the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) compared to SIC-free DFT results. The FLO-SIC HOMO–LUMO gap of the dianionic state is larger than that of the monoanionic state, which is consistent with experiment. Our results suggest a positive outlook of the FLO-SIC method in the description of magnetic exchange coupling within 3 d -element-based systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Super-expansive thermo-reversible interstitial solid solution of nanocrystal superlattices with mesogens

Designing superlattices of nanocrystals to mimic and extend the properties of atomic crystals has been a long-standing motivation in materials chemistry. Interstitial solid solutions, such as steel, are well-studied atomic lattices in which mobile components move among the interstices. These materials exhibit unique properties, including reversible structural changes and phase transitions. Interstitial solid solutions possess unique dynamic structures and reversible responses, which motivate the creation of their colloidal equivalents. Here, in this study, we report a fully thermo-reversible colloidal interstitial solid solution by combining liquid crystals and nanocrystals functionalized with promesogenic ligands. Mesogen molecules fill and diffuse among the interstices of a superlattice, resulting in a super-large thermal expansivity. The approach uses a modular design of interparticle interactions, allowing control of interparticle distance, microstructure and transition between crystallographic forms.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Quantifying the influence of different biocrust community states and their responses to warming temperatures on soil biogeochemistry in field and mesocosm studies

Biocrusts influence soil biogeochemistry by fixing carbon (C) and nitrogen (N) and through leachate inputs to soils. Functional rates can vary among biocrust community states and in response to edaphic properties, heterotrophic microbial activity, and global change. Using soils and biocrusts from the Colorado Plateau, Utah, USA, we aimed to quantify the influence of early-successional (ES) and late-successional (LS) biocrust community states on soil biogeochemistry. In a field setting, we found soil was less “fertile” under ES than LS biocrust, but ES biocrust had a relative influence 1.3 times greater than LS biocrust on soil fertility. Leachate collected from LS biocrust had, on average, 6 times more organic C and 1.7 times more dissolved N than ES biocrust, but concentrations of phosphorus (P) and inorganic N did not differ among the two biocrust types. Here, to disentangle influences of biocrusts and soil properties on biogeochemical pools, we constructed mesocosms from homogenized soil and left the surface bare or covered with ES or LS biocrust, before assignment to ambient or warmed (+5 °C) temperature treatments for 3 months. Multivariate biogeochemical properties differed among cover types, yet all exhibited losses of P, N, and organic C and nearly half of the biogeochemical variables considered did not differ among cover types. Mesocosms with LS biocrust retained more dissolved N, supported 8 additional, significant correlations among biogeochemical pools of the biocrust and mineral soil layer on average, and lost fewer of these correlations under warming. Overall, while soils under LS biocrusts were more fertile (i.e., had higher nutrient concentrations) than under ES, we did not find evidence implicating leachate as the primary driver of this difference. Biocrust influences on soil fertility were greater when mineral soil nutrients were in lower concentrations, highlighting the value of even incipient biocrusts for dryland functioning.

54 ENVIRONMENTAL SCIENCES↗