12 Search Results

The Li-CO₂ battery is a promising energy storage system with impressive theoretical specific energy and discharge capacity. Graphene-based single-atom catalysts (SACs) provide high surface area and long-term electrochemical reactivity and stability, making SACs among the most promising cathode catalysts for these batteries. However, current Li-CO₂ systems have high reaction barriers, slowing the reaction and greatly increasing the overpotential. Improvement of the discharge/charge energetics requires atomic-level innovations in cathode design, such as alterations to the catalyst chemical structure. In this paper, we propose enhancing the SAC by using a Ti metal center, which is found to deliver the highest electrochemical Limore » + CO₂ activity among 3d transition metal candidates. Furthermore, we propose cathode surface coating with ionic liquids, since these environments promote the formation of reaction intermediates in the electrochemical conversion process. Here, our work provides insights to optimize electrode design for high-performance Li-CO₂ batteries, which can open new avenues to recycle greenhouse gases and achieve enhanced renewable energy storage.« less

Seven types of plastics were pyrolyzed in a fluidized bed reactor: post-consumer recycled (PCR) high-density polyethylene (HDPE), PCR polypropylene (PP), virgin resins of varying molecular weights of HDPE, virgin resins of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and (PP). Pyrolysis produced non-condensable gases (C1-C3), liquid phase products (C4-C40), and solids (C40+ and chars), with alkane, alkene, alkadiene, aromatic, and multi-cycloaromatics as the predominant compounds. Polymer structure had the greatest impact on product distribution, with minimal influence from molecular weight. Branches in polyethylene (PE) acted as thermal defects initiating degradation. Higher branch density in PE led to increased concentrations ofmore » aromatics, branched alkanes, and internal alkenes. PP and PE exhibited distinct degradation mechanisms, with PP requiring less energy for decomposition and yielding more oil. Here, pyrolysis oil from PCR HDPE and PCR PP contained a higher proportion of branched compounds. Additives in PCR plastics may promote isomerization during pyrolysis.« less

δ-Valerolactone (DVL) is a five-carbon (C5) cyclic ester that can undergo ring-opening polymerization to yield high-performance, biocompatible polyesters. But current market prices of C5 chemicals like DVL are very high due to poor availability of C5 feedstock in petroleum. Herein, we demonstrate a novel route to DVL synthesis via dehydrogenation of biomass-derived 2-hydroxytetrahydropyran (HTHP) over Cu/SiO₂ without the use of toxic reagents. Since HTHP exists in thermal equilibrium with 3,4-dihydropyran (DHP) via dehydration, and with 2,2’-oxybis(tetrahydropyran) and 5-(tetrahydropyran-2-yloxy)pentanal via acetalization, we have also determined the thermochemistry (ΔH_rxn and ΔG_rxn) of each competing reaction using density functional theory (DFT) calculations atmore » the M06-2X/cc-pVTZ level. Finally, by developing a kinetic model of all 8 reactions involved, we have achieved 84% selectivity to DVL at 150°C in a packed bed reactor for over 72 hours of time on stream.« less

Recently, many topological materials have been discovered as promising electrocatalysts in chemical conversion processes and energy storage. However, it remains unclear how the topological electronic states specifically modulate the catalytic reaction. Here, the two-dimensional metal phthalocyanine-based covalent organic framework (MP_c-COF) is studied by ab initio thermodynamic calculations to clearly reveal the promotional effect on the electrochemical hydrogen evolution reaction (HER) induced by topological gapless bands (TGBs). We find that the prehydrogenated (and fluorinated) H₄CdPc-COF(F) shows the best HER performance, with 0.016 V (near zero) overpotential. By tracking changes to the electronic structure and free energy as the prehydrogenation and HERmore » processes occur, we are able to separately attribute the high HER efficiency in part due to the increase of the electron bath by donating electrons to the conjugated π bonds and also to the existence of TGBs. Specifically, the significant catalytic promotion by TGBs is proven to decrease the free energy by 0.218 eV to near zero. When the TGBs are destroyed, e.g., by replacing N with P and opening a band gap, the HER efficiency is reduced. As a result, this study opens avenues for deterministically harnessing topological band features to improve electrocatalysis.« less

The performance of proton-exchange membrane fuel cells is strongly dependent on the efficiency of the electrochemical oxygen reduction reaction (ORR). Here, we report both two-dimensional (4 monolayer, ML) and three-dimensional Bi (16 ML) (11̅0) facets deliver a strong correlation between nontrivial topological surface states and low electrochemical overpotential toward ORR. Both topological Bi (11̅0) film and slab have two slightly gapped (9–45 meV) Dirac cones with the invariant Z₂=1, derived from the parity products for the occupied states at four time-reversal invariant momentum points. By contrast, the Bi (110) film is stabilized as an ordinary insulator due to atomic buckling.more » The much lower thermodynamic ORR overpotential (η = 0.58 V) and higher H₂O selectivity by four steps of H⁺/e^– transfer are obtained on the topological Bi (11̅0) surface compared with the nontopological (110) facet (η = 0.84 V). This promotional effect can be attributed to the accumulation of topological surface bands (Bi 6p orbitals) near the Fermi energy, which provide stronger electronic transport channels along the surface Bi–Bi and Bi–O bonds. Finally, a 16 ML Bi (11̅0) slab is also constructed to simulate the topological (11̅0) surface of three-dimensional bulk Bi as a topological crystalline insulator (TCI). Furthermore, the consistent topological properties and slightly lower thermodynamic ORR overpotential (η = 0.53 V) are also observed on the thicker slab.« less

The inability to process many covalent organic frameworks (COFs) as thin films plagues their widespread utilization. Herein, a vapor-phase pathway for the bottom-up synthesis of a class of porphyrin-based COFs is presented. This approach allows integrating electrocatalysts made of metal-ion-containing COFs into the electrodes’ architectures in a single-step synthesis and deposition. By precisely controlling the metal sites at the atomic level, remarkable electrocatalytic performance is achieved, resulting in unprecedentedly high mass activity values. How the choice of metal atoms, i.e., cobalt and copper, can determine the catalytic activities of POR-COFs is demonstrated. The theoretical data proves that the Cu sitemore » is highly active for nitrate conversion to ammonia on the synthesized COFs.« less

Abstract The niobium oxide polymorph T -Nb ₂ O ₅ has been extensively investigated in its bulk form especially for applications in fast-charging batteries and electrochemical (pseudo)capacitors. Its crystal structure, which has two-dimensional (2D) layers with very low steric hindrance, allows for fast Li-ion migration. However, since its discovery in 1941, the growth of single-crystalline thin films and its electronic applications have not yet been realized, probably due to its large orthorhombic unit cell along with the existence of many polymorphs. Here we demonstrate the epitaxial growth of single-crystalline T -Nb ₂ O ₅ thin films, critically with the ionicmore » transport channels oriented perpendicular to the film’s surface. These vertical 2D channels enable fast Li-ion migration, which we show gives rise to a colossal insulator–metal transition, where the resistivity drops by 11 orders of magnitude due to the population of the initially empty Nb 4 d ⁰ states by electrons. Moreover, we reveal multiple unexplored phase transitions with distinct crystal and electronic structures over a wide range of Li-ion concentrations by comprehensive in situ experiments and theoretical calculations, which allow for the reversible and repeatable manipulation of these phases and their distinct electronic properties. This work paves the way for the exploration of novel thin films with ionic channels and their potential applications.« less

Waste plastics are an abundant feedstock for the production of renewable chemicals. Pyrolysis of waste plastics produces pyrolysis oils with high concentrations of olefins (>50 weight %). The traditional petrochemical industry uses several energy-intensive steps to produce olefins from fossil feedstocks such as naphtha, natural gas, and crude oil. In this work, we demonstrate that pyrolysis oil can be used to produce aldehydes through hydroformylation, taking advantage of the olefin functionality. These aldehydes can then be reduced to mono- and dialcohols, oxidized to mono- and dicarboxylic acids, or aminated to mono- and diamines by using homogeneous and heterogeneous catalysis. Thismore » route produces high-value oxygenated chemicals from low-value postconsumer recycled polyethylene. Here, we project that the chemicals produced by this route could lower greenhouse gas emissions ~60% compared with their production through petroleum feedstocks.« less

We use the DR9 of the DESI legacy imaging survey and SDSS galaxy groups to measure the conditional luminosity function (CLF) for groups with halo mass Mh ≥ 10¹² M_⊙ and redshift 0.01 ≤ z ≤ 0.08, down to a limiting r-band magnitude of M_r = –10 to –12. For given halo masses we measure the CLF for the total populations and for the red and blue populations classified using the (g – z) color. We find a clear faint-end upturn in the CLF of red satellites, with a slope α ≈ –1.8, which is almost independent of halo mass.more » This faint-end upturn is not seen for the blue and total populations. Our stellar population synthesis modeling shows that (g – z) provides a clean red/blue division and that red group galaxies defined by (g – z) are all dominated by old stellar populations. The fraction of old galaxies as a function of galaxy luminosity shows a minimum at M_r ~ –18, corresponding to M_* ~ 10^9.5 M_⊙. This scale is independent of halo mass and is comparable to the characteristic luminosity at which galaxies show a dichotomy in surface brightness and size, suggesting that the dichotomy in the old fraction and in galaxy structure may have a common origin. The rising of the old fraction at the faint end for Milky Way (MW)–sized halos is in good agreement with the quenched fraction measured for the MW/M31 system and from the ELVES survey. We discuss the implications of our results for the formation and evolution of low-mass galaxies and for the stellar mass functions of low-mass galaxies to be observed at high redshift.« less

The lithium–air battery, a powerful competitor to replace the traditional lithium-ion battery, has attracted increasing attention due to its extremely high theoretical energy density. However, its development is limited by the cathode and electrolyte properties, which should include high stability, conductivity, and electrocatalytic properties in oxygen-rich environments. Here, we employ a systematic first-principles study of Li–O₂ discharge and charge reactions on the Co₃O₄-based cathode with the assistance of dimethyl sulfoxide (DMSO) electrolyte. The structure, stability, and electronic properties of different surface reconstructions of the Co₃O₄(100) facet are investigated. In addition, the mechanisms and thermodynamic overpotentials of multi-step reactions between Li⁺/e^–more » and O₂ are provided, where lithium suboxide products (Li₂O₂ or Li₃O₂) are formed on the different Co₃O₄(100) terminations. The solvation shell of Li⁺ components in explicit DMSO solvent is investigated through ab initio molecular dynamics simulations. In general, we find that the Co₃O₄(100)-O (oxidized) surface is the most stable one under standard conditions, and the stable Li⁺ solvation structure is found in a tetrahedral Li(DMSO)₄⁺ shell in the DMSO-based electrolyte. Moreover, in the system of the Co₃O₄(100)-O cathode and DMSO electrolyte, the solution model pathway is energetically favorable for the Li–O₂ discharge reaction. It provides a low constant overpotential of 0.17 V during a long-term discharging process, thus causing the final toroid Li₂O₂ formation on the cathode. During the charging process, an overpotential of 0.36 V is required to rapidly decompose Li₂O₂.« less