Accelerating CO 2 Electroreduction to CO Over Pd Single-Atom Catalyst
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99 GENERAL AND MISCELLANEOUS↗
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Results for “dispersion function”
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Spectral function of fermions in a highly occupied non-Abelian plasma
We develop a method to obtain fermion spectral functions non-perturbatively in a non-Abelian gauge theory with high occupation numbers of gauge fields. After recovering the free field case, we extract the spectral function of fermions in a highly occupied non-Abelian plasma close to its non-thermal fixed point, i.e., in a self-similar regime of the non-equilibrium dynamics. We find good agreement with hard loop perturbation theory for medium-induced masses, dispersion relations and quasiparticle residues. We also extract the full momentum dependence of the damping rate of the collective excitations.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Silver Nanoparticles Functionalized Nanosilica Grown over Graphene Oxide for Enhancing Antibacterial Effect
The continuous growth of multidrug-resistant bacteria due to the overuse of antibiotics and antibacterial agents poses a threat to human health. Silver nanoparticles, silica-based materials, and graphene-based materials have become potential antibacterial candidates. In this study, we developed an effective method of enhancing the antibacterial property of graphene oxide (GO) by growing nanosilica (NS) of approximately 50 nm on the graphene oxide (GO) surface. The structures and compositions of the materials were characterized through powdered X-ray diffraction (P-XRD), transmission electron microscopy (TEM), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS), ultraviolet–visible spectroscopy (UV–VIS), dynamic light scattering (DLS), Raman spectroscopy (RM), Fourier-transform infrared spectroscopy (FTIR), Brunauer–Emmet–Teller (BET) surface area, and pore size determination. The silver nanoparticles (AgNPs) with an average diameter of 26 nm were functionalized on the nanosilica (NS) surface. The composite contained approximately 3% of silver nanoparticles. The silver nanoparticles on nanosilica supported over graphene oxide (GO/NS/AgNPs) exhibited a 7-log reduction of Escherichia coli and a 5.2-log reduction of Bacillus subtilis within one hour of exposure. Both GO/NS and GO/NS/AgNPs exhibited substantial antimicrobial effects against E. coli and B. subtilis.
36 MATERIALS SCIENCE↗
Evolution of the age-included nearest pair distribution in disperse multiphase flows
The age of the nearest particle pair is introduced as the difference between the current time and the most recent time when the nearest particle pair was formed. The evolution equation for the age-included nearest pair distribution function is derived. With the assumption of random destruction of the nearest particle pairs, the evolution equation predicts the exponential probability distribution of the ages of the nearest particle pairs. Particle-resolved numerical simulations with moving particles are performed to verify this prediction. The equation is then used to derive the evolution equation for the particle–fluid–particle (PFP) stress, which is known to be related to hyperbolicity of the two-fluid equations. It is found that the relaxation time of the age probability distribution is also the relaxation time for the PFP stress. Guided by the closure terms in the PFP stress evolution equation, we study kinematics of the nearest particle pairs in the particle-resolved simulations for flows caused by sedimentation of the particles with initially isotropic and homogeneous particle distributions. At the steady states, the particle Reynolds numbers are around 20. Anisotropy and inhomogeneity of particle distributions are seen to develop in these flows. The mean distances to the nearest particles and evolution of the distribution of the Voronoi cell volumes are studied. We also found the PFP stress is closely related to the changes in these inter-particle scale quantities.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Preactivated zeolite nanosheet plate-tiled membrane on porous PVDF film: Synthesis and study of proton-selective ion conduction
Preactivated MFI zeolite nanosheet plates (ZNPs) with large areas (~2.0 × 2.0 μm 2 ) and nanometer thicknesses (~60 nm) were prepared directly in liquid-dispersed state. The individual ZNP was a stack of 4-nm-thick single crystalline zeolite nanosheets (ZNs) interlinked by Si–O–Si bonds between neighboring ZN surfaces. The dispersed open-pore ZNPs allowed formulating suspensions for tiling ZNP membranes on polymer substrates without requiring post-coating activation. A pinhole-free ZNP-tiled (ZNPT) membrane has been achieved on macroporous PVDF film by a self-repairing vacuum-assisted filtration coating method. The resultant ZNPT layer was ~500 nm-thick consisting of about 7 ZNP layers with inter-ZNP width and inter-ZNP entrance porosity around 9 nm and 2%, respectively. The ZNPT-PVDF membrane exhibited high selectivity to proton transport over vanadyl ion and low resistances to proton conduction in aqueous solutions. The membrane also demonstrated to function as an efficient ion separator for the vanadium redox flow battery. The reported synthesis of preactivated ZNP suspension may overcome the major hurdle to realizing polymer-supported ZN membranes, which is the inefficiency of existing methods in obtaining readily dispersible open-pore ZNs. Finally, the ZNPT-PVDF membrane can be a more affordable and sustainable alternative to the Nafion-based ion separation membranes.
36 MATERIALS SCIENCE↗
Transport of colloidal particles in microscopic porous medium analogs with surface charge heterogeneity: experiments and fundamental role of single-bead deposition
Understanding colloid transport in subsurface environments is challenging due to complex interactions between colloids, ground water, and porous media over several length scales. Here, we study the transport of colloidal particles through bead-assembled microfluidic porous media analogs (PMAs) with surface charge heterogeneity. The pore-scale dynamics of colloidal particle deposition were measured, as well as the breakthrough curves (BTC) and retention profiles (RP) of deposited colloidal particles at the scale of the entire PMA. From pore-scale experiments, the maximum surface coverage (?max = 0.51) was measured directly, from which the surface blocking function and deposition coefficient (kpore = 3.56 s-1) were obtained. Using these pore-scale parameters, the transport of colloidal particles was modeled using a one-dimensional advection-dispersion equation under the assumption of irreversible adsorption between oppositely charged beads and colloids, showing good agreement with experimental data. This work presents a new approach to fabricate chemically heterogeneous porous media in a microfluidic device that enables direct measurements of pore-scale colloidal deposition. The approach allows a quantitative prediction of colloidal breakthrough and retention via coupling of direct measurements and an advection-dispersion-deposition model.
Guo, Yang↗
Strain enhances the activity of molecular electrocatalysts via carbon nanotube supports
Abstract Support-induced strain engineering is useful for modulating the properties of two-dimensional materials. However, controlling strain of planar molecules is technically challenging due to their sub-2 nm lateral size. Additionally, the effect of strain on molecular properties remains poorly understood. Here we show that carbon nanotubes (CNTs) are ideal substrates for inducing optimum properties through molecular curvature. In a tandem-flow electrolyser with monodispersed cobalt phthalocyanine (CoPc) on single-walled CNTs (CoPc/SWCNTs) for CO 2 reduction, we achieve a methanol partial current density of >90 mA cm −2 with >60% selectivity, surpassing wide multiwalled CNTs at 16.6%. We report vibronic and X-ray spectroscopies to unravel the distinct local geometries and electronic structures induced by the strong molecule–support interactions. Grand canonical density functional theory confirms that curved CoPc/SWCNTs improve *CO binding to enable subsequent reduction, whereas wide multiwalled CNTs favour CO desorption. Our results show the important role of SWCNTs beyond catalyst dispersion and electron conduction.
Chemistry↗
Black hole and galaxy co-evolution in radio-loud active galactic nuclei at z ~ 0.3–4
The relation between the mass of the supermassive black hole (SMBH) in the center of galaxies and their bulge mass or central velocity dispersion is well known. This suggests a coevolution between the SMBHs and their galaxy hosts. Our aim is to study this relation, specifically, for radio loud galaxies, and as a function of redshift z. We selected a sample of 42 radio galaxies and active galactic nuclei (AGN) with broad emission lines and spectroscopic redshifts between z = 0.3 - 4 by cross-matching the low radio frequency sources from Very Large Array (VLA) FIRST with spectroscopically confirmed galaxies from wide-field surveys, including Sloan Digital Sky Survey (SDSS) DR14 ugriz and Dark Energy Survey (DES) DR2 grzY in the optical, Wield Infrared Survey Explorer (WISE), and the Galaxy And Mass Assembly (GAMA) spectroscopic survey. We characterized the stellar mass (M $\star$ ), star formation, and black hole properties (mass of the central SMBH, Eddington ratio η, and jet power, Q jet ). The relation between SMBH mass, M $\star$ , η, and z is placed into context by comparing them with scaling relations (M BH –M $\star$ , M BH /M $\star$ –z, M BH –Q jet , and Q jet –η) from the literature. On the basis of a multiwavelength spectral energy distribution modeling, our radio sources are broadly consistent with being on the star-forming main sequence. They have sub-Eddington accretion rates, η ≃ 1% on average, as typically found in type I AGN, while higher accretion rates favor more powerful jets to be launched by the central engine. We find overmassive SMBHs in (17 ± 5)% of our radio sources, similarly to previous studies on nearby early-type galaxies. Altogether, an evolutionary scenario in which radio-mode AGN feedback regulates the accretion onto the SMBHs and the stellar mass assembly of the radio sources is discussed, which may explain the observed phenomenology. This pilot study represents a benchmark for future studies using wide-field surveys such as those with Euclid and the Vera Rubin Observatory.
79 ASTRONOMY AND ASTROPHYSICS↗
Plasmons in two-dimensional topological insulators
Here, we analyze collective excitations in models of two-dimensional topological insulators using the random phase approximation. In a two-dimensional extension of the Su-Schrieffer-Heeger model, edge plasmonic excitations with induced charge-density distributions localized at the boundaries of the system are found in the topologically nontrivial phase, dispersing similarly as one-dimensional bulk plasmons in the conventional Su-Schrieffer-Heeger chain. For two-dimensional bulk collective modes, we reveal regimes of enhanced interband wave function correlations, leading to characteristic hardening and softening of inter- and intraband bulk plasmonic branches, respectively. In the two-dimensional Haldane Chern insulator model, chiral, unidirectional edge plasmons in nano-ribbon architectures are observed, which can be characterized by an effective Coulomb interaction cross section. Bulk collective excitations in the two-dimensional Haldane model are shown to be originated by single-particle band structure details in different topological phases.
2-dimensional systems↗
SDSS-IV MaNGA: Modeling the Spectral Line-spread Function to Subpercent Accuracy
The Sloan Digital Sky Survey IV Mapping Nearby Galaxies at APO (MaNGA) program has been operating from 2014 to 2020, and has now observed a sample of 9269 galaxies in the low redshift universe (z ∼ 0.05) with integral-field spectroscopy. With rest-optical (λλ0.36–1.0 μm) spectral resolution R ∼ 2000 the instrumental spectral line-spread function (LSF) typically has 1σ width of about 70 km s{sup −1}, which poses a challenge for the study of the typically 20–30 km s{sup −1} velocity dispersion of the ionized gas in present-day disk galaxies. In this contribution, we present a major revision of the MaNGA data pipeline architecture, focusing particularly on a variety of factors impacting the effective LSF (e.g., under-sampling, spectral rectification, and data cube construction). Through comparison with external assessments of the MaNGA data provided by substantially higher-resolution R ∼ 10,000 instruments, we demonstrate that the revised MPL-10 pipeline measures the instrumental LSF sufficiently accurately (≤0.6% systematic, 2% random around the wavelength of Hα) that it enables reliable measurements of astrophysical velocity dispersions σ {sub Hα} ∼ 20 km s{sup −1} for spaxels with emission lines detected at signal-to-noise ratio > 50. Velocity dispersions derived from [O II], Hβ, [O III], [N II], and [S II] are consistent with those derived from Hα to within about 2% at σ {sub Hα} > 30 km s{sup −1}. Although the impact of these changes to the estimated LSF will be minimal at velocity dispersions greater than about 100 km s{sup −1}, scientific results from previous data releases that are based on dispersions far below the instrumental resolution should be reevaluated.
47 OTHER INSTRUMENTATION↗
Aqueous dispersions, coating compositions formed with aqueous dispersions, and multi-layer coatings
An aqueous dispersion includes an aqueous medium and self-crosslinkable core-shell particles dispersed in the aqueous medium. The core-shell particles include (1) a polymeric core at least partially encapsulated by (2) a polymeric shell having urethane linkages, keto and/or aldo functional groups, and hydrazide functional groups. Further, the polymeric core is covalently bonded to at least a portion of the polymeric shell.
36 MATERIALS SCIENCE↗
Enzymatic Nitrogen Insertion into Unactivated C–H Bonds
Selective functionalization of aliphatic C–H bonds, ubiquitous in molecular structures, could allow ready access to diverse chemical products. While enzymatic oxygenation of C–H bonds is well established, the analogous enzymatic nitrogen functionalization is still unknown; nature is reliant on pre-oxidized compounds for nitrogen incorporation. Likewise, synthetic methods for selective nitrogen derivatization of unbiased C–H bonds remain elusive. In this work, new-to-nature heme-containing nitrene transferases were used as starting points for the directed evolution of enzymes to selectively aminate and amidate unactivated C(sp3)–H sites. The desymmetrization of methyl- and ethylcyclohexane with divergent site selectivity is offered as demonstration. The evolved enzymes in these lineages are highly promiscuous and show activity towards a wide array of substrates, providing a foundation for further evolution of nitrene transferase function. Computational studies and kinetic isotope effects (KIEs) are consistent with a stepwise radical pathway involving an irreversible, enantiodetermining hydrogen atom transfer (HAT), followed by a lower-barrier diastereoselectivity determining radical rebound step. In-enzyme molecular dynamics (MD) simulations reveal a predominantly hydrophobic pocket with favorable dispersion interactions with the substrate. Here, by offering a direct path from saturated precursors, these enzymes present a new biochemical logic for accessing nitrogen-containing compounds.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Phonons in Copper Diphosphide (CuP 2 ): Raman Spectroscopy and Lattice Dynamics Calculations
Copper diphosphide (CuP 2 ) is an emerging binary semiconductor with promising properties for energy conversion and storage applications. While functionality and possible applications of CuP 2 have been studied, there is a curious gap in the investigation of its vibrational properties. In this work, we provide a reference Raman spectrum of CuP 2 , with a complete analysis of all Raman active modes from both experimental and theoretical perspectives. Raman measurements have been performed on polycrystalline CuP 2 thin films with close to stoichiometric composition. Detailed deconvolution of the Raman spectrum with Lorentzian curves has allowed identification of all theoretically predicted Raman active modes (9A g and 9B g ), including their positions and symmetry assignment. Furthermore, calculations of the phonon density of states (PDOS), as well as the phonon dispersions, provide a microscopic understanding of the experimentally observed phonon lines, in addition to the assignment to the specific lattice eigenmodes. We further provide the theoretically predicted positions of the infrared (IR) active modes, along with the simulated IR spectrum from density functional theory (DFT). Overall good agreement is found between the experimental and DFT-calculated Raman spectra of CuP 2 , providing a reference platform for future investigations on this material.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Enhanced Catalytic Performance of a Ce/V Oxo Cluster through Confinement in Mesoporous SBA-15
To increase catalytic efficiency, mesoporous supports have been widely applied to immobilize well-defined metal oxide clusters due to their ability to stabilize highly dispersed clusters. Here, for this study, a redox-active heterometallic Ce 12 V 6 -oxo cluster (CeV) was first presynthesized and then incorporated into mesoporous silica, SBA-15, via a straightforward impregnation method. Scanning transmission electron microscopy (STEM) and Fourier transform infrared spectroscopy (FTIR), in concert with scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDS), verified the successful introduction of the CeV cluster inside the pore of SBA-15. The 51 V magic angle spinning solid-state nuclear magnetic resonance ( 51 V MAS NMR) spectroscopy and differential pair distribution function (dPDF) analysis confirmed the structural integrity of the CeV cluster inside the SBA-15. The composite was then benchmarked for liquid-phase oxidation of 2-chloroethyl ethyl sulfide (CEES) under mild conditions and gas-phase oxidative dehydrogenation (ODH) of propane under high temperatures (up to 550 °C). The catalytic reactivity results demonstrated 8- and 14-fold increase in turnover frequency (TOF) values of the composite (CeV@10SBA-2) than the bulk CeV cluster under the same conditions for CEES oxidation and ODH, respectively. These results highlight the improved reactivity of the catalytically active CeV cluster as attributed to the higher dispersion of the discrete cluster upon immobilization within the SBA-15 support.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Synergizing a Large Ordinary Nernst Effect and Axis‐Dependent Conduction Polarity in Flat Band KMgBi Crystals
The exploration of quantum materials in which an applied thermo/electrical/magnetic field along one crystallographic direction produces an anisotropic response has led to unique functionalities. Along these lines, KMgBi is a layered, narrow gap semiconductor near a critical state between multiple Dirac phases due to the presence of a flat band near the Fermi level. The valence band is highly anisotropic with minimal cross-plane dispersion, which, in combination with an isotropic conduction band, enables axis-dependent conduction polarity. Thermopower and Hall measurements indicate dominant p-type conduction along the cross-plane direction, and n-type conduction along the in-plane direction, leading to a significant zero-field transverse thermoelectric response when the heat flux is at an angle to the principal crystallographic directions. Additionally, a large Ordinary Nernst effect (ONE) is observed with an applied field. It arises from the ambipolar term in the Nernst effect, whereby the Lorentz force on electrons and holes makes them drift in opposite directions so that the resulting Nernst voltage becomes a function of the difference between their partial thermopowers, greatly enhancing the ONE. It is proven that axis-dependent polarity can synergistically enhance the ONE, in addition to leading to a zero-field transverse thermoelectric performance.
36 MATERIALS SCIENCE↗
An accurate perturbative approach to redshift space clustering of biased tracers in modified gravity
We extend the scale-dependent Gaussian Streaming Model (GSM) to produce analytical predictions for the anisotropic redshift-space correlation function for biased tracers in modified gravity models. Employing the Convolution Lagrangian Perturbation Theory (CLPT) re-summation scheme, with a local Lagrangian bias schema provided by the peak-background split formalism, we predict the necessary ingredients that enter the GSM, the real-space halo pairwise velocity and the pairwise velocity dispersion. We further consider effective field theory contributions to the pairwise velocity dispersion in order to model correctly its large scale behavior. We apply our method on two widely-considered modified gravity models, the chameleon-screened ƒ(R) Hu-Sawicki model and the nDGP Vainshtein model and compare our predictions against state-of-the-art N-body simulations for these models. We demonstrate that the GSM approach to predict the monopole and the quadrupole of the redshift-space correlation function for halos, gives very good agreement with the simulation data, for a wide range of screening mechanisms, levels of screening and halo masses at z = 0.5 and z = 1. Our work shows the applicability of the GSM, for cosmologies beyond GR, demonstrating that it can serve as a powerful predictive tool for the next stage of cosmological surveys like DESI, Euclid, LSST and WFIRST.
79 ASTRONOMY AND ASTROPHYSICS↗
Surface facet dependence of competing alloying mechanisms
Metal alloys are ubiquitous in many branches of heterogeneous catalysis, and it is now fairly well established that the local atomic structure of an alloy can have a profound influence on its chemical reactivity. While these effects can be difficult to probe in nanoparticle catalysts, model studies using well defined single crystal surfaces alloyed with dopants enable these structure–function correlations to be drawn. The first step in this approach involves understanding the alloying mechanism and the type of ensembles formed. In this study, we examined the atomic structure of RhCu single-atom alloys formed on Cu(111), Cu(100), and Cu(110) surfaces. Our results show a striking difference between Rh atoms alloying in Cu(111) vs the more open Cu(100) and Cu(110) surface facets. Unlike Cu(111) on which Rh atoms preferentially place-exchange with Cu atoms in the local regions above step edges leaving the majority of the Cu surface free of Rh, highly dispersed, homogeneous alloys are formed on the Cu(100) and (110) surfaces. These dramatically different alloying mechanisms are understood by quantifying the energetic barriers for atomic hopping, exchange, swapping, and vacancy filling events for Rh atoms on different Cu surfaces through theoretical calculations. Density functional theory results indicate that the observed differences in the alloying mechanism can be attributed to a faster hopping rate, relatively high atomic exchange barriers, and stronger binding of Rh atoms in the vicinity of step edges on Cu(111) compared to Cu(110) and Cu(100). Furthermore, these model systems will serve as useful platforms for examining structure sensitive chemistry on single-atom alloys.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Combining four-point bending and corrosion to map stress-dependent corrosion susceptibility of 316H stainless steel in FLiNaK
Understanding the effect of stress on the corrosion of steels in molten salts is important for material screening and safety assessment of molten salt reactors. We present a method that combines four-point bending with corrosion testing, enabling the mapping of corrosion susceptibility as a function of local stress from a single specimen. Guided by finite element analysis, a four-point bending setup was used to bend a 316H stainless-steel bar under controlled elastic stress during a 100-hour exposure in FLiNaK at 700 °C. Post-exposure characterization using scanning electron microscopy and energy-dispersive X-ray spectroscopy revealed a pronounced correlation between stress and corrosion. Regions under tensile stress exhibited significantly deeper attack depths and greater chromium depletion along grain boundaries, whereas compressive zones showed shallower corrosion cracks. The stress effect is attributed to stress concentration under tensile loading, which promotes chromium dissolution and crack propagation. This technique can be readily applied to other structural alloys, enabling quantitative measurement of corrosion susceptibility as a function of local stress.
316H↗