The role of oxygen vacancies in carbon dioxide electroreduction remains somewhat unclear. Here we construct a model of oxygen vacancies confined in atomic layer, taking the synthetic oxygen-deficient cobalt oxide single-unit-cell layers as an example. Density functional theory calculations demonstrate the main defect is the oxygen(II) vacancy, while X-ray absorption fine structure spectroscopy reveals their distinct oxygen vacancy concentrations. Proton transfer is theoretically/experimentally demonstrated to be a rate-limiting step, while energy calculations unveil that the presence of oxygen(II) vacancies lower the rate-limiting activation barrier from 0.51 to 0.40 eV via stabilizing the formate anion radical intermediate, confirmed by the lowered onset potential from 0.81 to 0.78 V and decreased Tafel slope from 48 to 37 mV dec−1. Hence, vacancy-rich cobalt oxide single-unit-cell layers exhibit current densities of 2.7 mA cm−2 with ca. 85% formate selectivity during 40-h tests. This work establishes a clear atomic-level correlation between oxygen vacancies and carbon dioxide electroreduction.
Electroreduction of CO2 into hydrocarbons could contribute to alleviating energy crisis and global warming. However, conventional electrocatalysts usually suffer from low energetic efficiency and poor durability. Herein, atomic layers for transition-metal oxides are proposed to address these problems through offering an ultralarge fraction of active sites, high electronic conductivity, and superior structural stability. As a prototype, 1.72 and 3.51 nm thick Co3O4 layers were synthesized through a fast-heating strategy. The atomic thickness endowed Co3O4 with abundant active sites, ensuring a large CO2 adsorption amount. The increased and more dispersed charge density near Fermi level allowed for enhanced electronic conductivity. The 1.72 nm thick Co3O4 layers showed over 1.5 and 20 times higher electrocatalytic activity than 3.51 nm thick Co3O4 layers and bulk counterpart, respectively. Also, 1.72 nm thick Co3O4 layers showed formate Faradaic efficiency of over 60% in 20 h.
In a semimetal, both electrons and holes contribute to the density of states at the Fermi level. The small band overlaps and multiband effects engender novel electronic properties. We show that a moderate hydrostatic pressure effectively suppresses the band gap in the elemental semiconductor black phosphorus. An electronic topological transition takes place at approximately 1.2 GPa, above which black phosphorus evolves into a semimetal state that is characterized by a colossal positive magnetoresistance and a nonlinear field dependence of Hall resistivity. The Shubnikov-de Haas oscillations detected in magnetic field reveal the complex Fermi surface topology of the semimetallic phase. In particular, we find a nontrivial Berry phase in one Fermi surface that emerges in the semimetal state, as evidence of a Dirac-like dispersion. The observed semimetallic behavior greatly enriches the material property of black phosphorus and sets the stage for the exploration of novel electronic states in this material.
We provide a perspective on polymer glass formation, with an emphasis on models in which the fluid entropy and collective particle motion dominate the theoretical description and data analysis. The entropy theory of glass formation has its origins in experimental observations relating to correlations between the fluid entropy and liquid dynamics going back nearly a century ago, and it has entered a new phase in recent years. We first discuss the dynamics of liquids in the high-temperature Arrhenius regime, where transition state theory is formally applicable. We then summarize the evolution of the entropy theory from a qualitative framework for organizing and interpreting temperature-dependent viscosity data by Kauzmann to the formulation of a hypothetical “ideal thermodynamic glass transition” by Gibbs and DiMarzio, followed by seminal measurements linking entropy and relaxation by Bestul and Chang and the Adam–Gibbs (AG) model of glass formation rationalizing the observations of Bestul and Chang. These developments laid the groundwork for the generalized entropy theory (GET), which merges an improved lattice model of polymer thermodynamics accounting for molecular structural details and enabling the analytic calculation of the configurational entropy with the AG model, giving rise to a highly predictive model of the segmental structural relaxation time of polymeric glass-forming liquids. The development of the GET has occurred in parallel with the string model of glass formation in which concrete realizations of the cooperatively rearranging regions are identified and quantified for a wide range of polymeric and other glass-forming materials. The string model has shown that many of the assumptions of AG are well supported by simulations, while others are certainly not, giving rise to an entropy theory of glass formation that is largely in accord with the GET. As the GET and string models continue to be refined, these models progressively grow into a more unified framework, and this Perspective reviews the present status of development of this promising approach to the dynamics of polymeric glass-forming liquids.
The magneto‐thermoelectric figure of merit (ZT) in crystals of the topological Dirac semimetal Cd3As2 with different carrier concentrations is studied. The ZTs for all the crystals increase with the temperature and show maxima at high temperatures. Meanwhile, the temperatures corresponding to the ZT maxima increase with the carrier concentration. The limit to the improvement in ZT(T) at high temperature could be related to the unusual large enhancement in thermal conductivity at elevated temperatures. The bipolar effect and Dirac liquid behavior are presented as processes possibly responsible for the peculiar behavior of the thermal conductivity. Applying a transverse magnetic field initially leads to a dramatic enhancement and, subsequently, to a slight reduction in ZT for all the crystals. The maximum ZT achieved in a magnetic field increases with the carrier concentration and reaches 1.24 at 450 K in a magnetic field of 9 T for the crystal with the highest carrier concentration. It is expected that this work will be beneficial to the current interests in optimizing the thermoelectric properties of quantum topological materials.
We study living polymerization initiated from concave surfaces. We clarify that, depending on different criteria for ceasing the reaction, different relationships between grafted chain polydispersity index and the grafting surface curvature can be categorized. The average molecular weight of the grafted chains monotonically decreases as the grafting surface curvature increases. These results shed light on better control and design of functional porous materials for use in bioimplanting or chemical sensors.
We perform lattice Monte Carlo simulation using the bond-fluctuation model to examine the conformation and dynamic properties of a single small flexible ring polymer in the matrix of linear chains as functions of the degree of polymerization of the linear chains. The average conformation properties as gauged by the mean-square radius of gyration and asphericity parameter are insensitive to the chain length for all the chain lengths examined ͑30, 100, 300, and 1000͒. However, in the longer chain ͑300 and 1000͒ samples, there is an increased spread in the distribution of the value of these quantities, suggesting structural heterogeneity. The center-of-mass diffusion of the ring shows a rapid decrease with increasing chain length followed by a more gradual change for the two longer chain systems. In these longer chain systems, a wide spread in the value of the apparent self-diffusion coefficient is also observed, as well as qualitatively different square displacement trajectories among the different samples, suggesting heterogeneity in the dynamics. A primitive path analysis reveals that in these long chain systems, the ring can exist in topologically distinct states with respect to threading by the linear chains. Threading by the linear chain can dramatically slow down and in some cases stall the diffusive motion of the ring. We argue that the life times for these topological conformers can be longer than the disentanglement time of the linear chain matrix, so that the ring exhibits nonergodic behavior on time scales less or comparable to the life time of these conformers. Our results suggest a picture of the ring diffusion as one where the diffusion path consists of distinctive segments, each corresponding to a different conformer, with slow interconversion between the different conformers.
To achieve simulations on large spatial and temporal scales with high molecular chemical specificity, a hybrid particle-field method was proposed recently. This method is developed by combining molecular dynamics and self-consistent field theory (MD-SCF). The MD-SCF method has been validated by successfully predicting the experimentally observable properties of several systems. Here we propose an efficient scheme for the inclusion of electrostatic interactions in the MD-SCF framework. In this scheme, charged molecules are interacting with the external fields that are self-consistently determined from the charge densities. This method is validated by comparing the structural properties of polyelectrolytes in solution obtained from the MD-SCF and particle-based simulations. Moreover, taking PMMA-b-PEO and LiCF3SO3 as examples, the enhancement of immiscibility between the ion-dissolving block and the inert block by doping lithium salts into the copolymer is examined by using the MD-SCF method. By employing GPU-acceleration, the high performance of the MD-SCF method with explicit treatment of electrostatics facilitates the simulation study of many problems involving polyelectrolytes.
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