Site-Selective Deposition of Metal-Organic Frameworks on Gold Nanobipyramids for Surface-Enhanced Raman Scattering.

Site-selective deposition of metal-organic frameworks (MOFs) on metal nanocrystals has remained challenging because of the difficult control of the nucleation and growth of MOFs. Herein we report on a facile wet-chemistry approach for the selective deposition of zeolitic imidazolate framework-8 (ZIF-8) on anisotropic Au nanobipyramids (NBPs) and nanorods. ZIF-8 is selectively deposited at the ends and waist and around the entire surface of the elongated Au nanocrystals.

First-principles prediction of infrared phonon and dielectric function in biaxial hyperbolic van der Waals crystal α-MoO.

Layered biaxial hyperbolic molybdenum trioxide (α-MoO) with weak van der Waals (vdW) interlayer bonding recently received extensive attention due to its anisotropic dielectric response to infrared (IR) radiation, which couples to the lattice vibrations and allows for manipulating the radiative energy transport. However, the understanding of IR-active phonon modes and dielectric function of it has not yet been fully achieved. Here, by utilizing mode-level first-principles analysis based on density functional theory (DFT), the phonon modes contributing to the IR dielectric response of α-MoO are fully determined.

Advances in Electrochemical Ammonia Synthesis Beyond the Use of Nitrogen Gas as a Source.

Electrocatalytic reduction of dinitrogen has emerged as a new strategy for ammonia synthesis. Despite being environmentally benign and energy-saving, it suffers from low conversion efficiency and short yield of ammonia because of the challenges of activating the inert N≡N bond at room temperature and atmospheric pressure. As a result of this, researchers proposed to reduce the nitrogenous species, one category of air and water pollutants, into valuable ammonia.

Ion exchange in atomically thin clays and micas.

The physical properties of clays and micas can be controlled by exchanging ions in the crystal lattice. Atomically thin materials can have superior properties in a range of membrane applications, yet the ion-exchange process itself remains largely unexplored in few-layer crystals. Here we use atomic-resolution scanning transmission electron microscopy to study the dynamics of ion exchange and reveal individual ion binding sites in atomically thin and artificially restacked clays and micas.

Effect of Precursor Nature and Sol-Gel Synthesis Conditions on TiO Aerogel's Structure.

The aim of this investigation was to synthesize high porosity TiO aerogel by applying sol-gel and subcritical drying methods and to identify the influence of reagent's nature and synthesis conditions on their structural and optical properties. Methods of XRD, FT-IR, BET, STA, SEM, and UV-vis were applied to investigate and compare the properties of synthesized TiO aerogels and to determine the most effective synthesis route. The structural parameters of the synthesized materials can be varied by changing the precursor type (titanium (IV), isopropoxide (TIP), or tetrabutylorthotitanate (TBOT)) and the nature of the solvent used for additional exchange (-hexane (nH), cyclohexane (CH), or diethyl ether (DE)).

Activity and Mechanism Mapping of Photocatalytic NO Conversion on the Anatase TiO(101) Surface.

NO emission heavily affects our environment and human health. Photocatalytic denitrification (deNO) attracted much attention because it is low-cost and nonpolluting, but undesired nitrite and nitrate were produced in reality, instead of harmless N. Unveiling the active sites and the photocatalytic mechanism is very important to improve the process.

Phononic Thermal Transport along Graphene Grain Boundaries: A Hidden Vulnerability.

While graphene grain boundaries (GBs) are well characterized experimentally, their influence on transport properties is less understood. As revealed here, phononic thermal transport is vulnerable to GBs even when they are ultra-narrow and aligned along the temperature gradient direction. Non-equilibrium molecular dynamics simulations uncover large reductions in the phononic thermal conductivity (κ ) along linear GBs comprising periodically repeating pentagon-heptagon dislocations.

Stress-Strain and Stress-Relaxation Behaviors of Solution-Coated Layers Composed of Block Copolymers Mixed with Tackifiers.

The relationship between the mechanical properties and the structure of block copolymers mixed with tackifiers whose relative solubility to the respective components of block copolymers differs was examined. Coated layers were prepared by solution coating using a block copolymer composed of polystyrene (PS) and polyisoprene (PI), which forms spherical microdomains of PS in the PI matrix, mixed with three types of tackifiers: aliphatic (C5) resin, aliphatic-aromatic (C5-C9) resin, and rosin ester (RE) resin. Furthermore, the correlation between the changes in the nanostructure and mechanical properties including the stress-relaxation behaviors was clarified by two-dimensional small-angle X-ray scattering measurement.

Tracking Electron Dynamics of Single Molecules in Scanning Tunneling Microscopy Junctions with Laser Pulses.

On the basis of real-time simulations, we devise a method to extend the capability of scanning tunneling microscopy (STM) to track the electronic dynamics of molecules on a material's surface with the ultrafast temporal resolution of laser pulses. The intrinsic mechanism of visualization of electronic dynamics by measuring tunneling charge is attributed to the interference between the electronic oscillations stimulated by pump and probe pulses. The charge-transfer rate from molecule to the surrounding environment can be estimated with the decay time of electronic dynamics, which can also be detected by measuring the tunneling charge across the STM junction.

Using DFTB to Model Photocatalytic Anatase-Rutile TiO Nanocrystalline Interfaces and Their Band Alignment.

Band alignment effects of anatase and rutile nanocrystals in TiO powders lead to electron-hole separation, increasing the photocatalytic efficiency of these powders. While size effects and types of possible alignments have been extensively studied, the effect of interface geometries of bonded nanocrystal structures on the alignment is poorly understood. To allow conclusive studies of a vast variety of bonded systems in different orientations, we have developed a new density functional tight-binding parameter set to properly describe quantum confinement in nanocrystals.

Allosteric regulation in CRISPR/Cas1-Cas2 protospacer acquisition mediated by DNA and Cas2.

Cas1 and Cas2 are highly conserved proteins across clustered-regularly-interspaced-short-palindromic-repeat-Cas systems and play a significant role in protospacer acquisition. Based on crystal structure of twofold symmetric Cas1-Cas2 in complex with dual-forked protospacer DNA (psDNA), we conducted all-atom molecular dynamics simulations to study the psDNA binding, recognition, and response to cleavage on the protospacer-adjacent-motif complementary sequence, or PAMc, of Cas1-Cas2. In the simulation, we noticed that two active sites of Cas1 and Cas1' bind asymmetrically to two identical PAMc on the psDNA captured from the crystal structure.

Revealing generation, migration, and dissociation of electron-hole pairs and current emergence in an organic photovoltaic cell.

Using an innovative quantum mechanical method for an open quantum system, we observe in real time and space the generation, migration, and dissociation of electron-hole pairs, transport of electrons and holes, and current emergence in an organic photovoltaic cell. Ehrenfest dynamics is used to study photoexcitation of thiophene:fullerene stacks coupled with a time-dependent density functional tight-binding method. Our results display the generation of an electron-hole pair in the donor and its subsequent migration to the donor-acceptor interface.

How to Utilize Excited Plasmon Energy Efficiently.

Plasmonic nanoparticles can concentrate electromagnetic fields at the nanoscale and function as a powerful intermediary to enhance light-matter interactions. They have been widely employed for solar energy harvesting, photocatalysis, medicine, sensing, imaging, spectroscopy, optics, and optoelectronics. In this Perspective, we provide a brief overview of research progress in the utilization of excited plasmon energy, with emphasis on the charge- and energy-transfer processes.

Facet- and Gas-Dependent Reshaping of Au Nanoplates by Plasma Treatment.

The reshaping of metal nanocrystals on substrates is usually realized by pulsed laser irradiation or ion-beam milling with complex procedures. In this work, we demonstrate a simple method for reshaping immobilized Au nanoplates through plasma treatment. Au nanoplates can be reshaped gradually with nearly periodic right pyramid arrays formed on the surface of the nanoplates.

Revealing atomic-scale molecular diffusion of a plant-transcription factor WRKY domain protein along DNA.

Transcription factor (TF) target search on genome is highly essential for gene expression and regulation. High-resolution determination of TF diffusion along DNA remains technically challenging. Here, we constructed a TF model system using the plant WRKY domain protein in complex with DNA from crystallography and demonstrated microsecond diffusion dynamics of WRKY on DNA by employing all-atom molecular-dynamics (MD) simulations.

Electric Field Tunable Ultrafast Interlayer Charge Transfer in Graphene/WS Heterostructure.

Van der Waals heterostructures composed of two-dimensional materials offer an unprecedented control over their properties and have attracted tremendous research interest in various optoelectronic applications. Here, we study the photoinduced charge transfer in graphene/WS heterostructure by time-dependent density functional theory molecular dynamics. Our results show that holes transfer from graphene to WS two times faster than electrons, and the occurrence of interlayer charge transfer is found correlated with vibrational modes of graphene and WS.

Ultralow Thermal Conductivity in Two-Dimensional MoO.

Monolayer molybdenum trioxide (MoO) is an emerging two-dimensional (2D) material with high electrical conductivity but unexplored thermal conductivity. Using first-principles calculations and a Boltzmann transport theoretical framework, we predict a record low room-temperature phonon thermal conductivity (κ) of 1.57 and 1.

Two-Dimensional Magnetic Anionic Electrons in Electrides: Generation and Manipulation.

Introducing magnetism to anionic electrons (AE) of electrides, especially for those confined in two-dimensional (2D) interlayer spaces, could provide a promising way to generate 2D spin-polarized free electron gas. However, the realization of this is challenging. Here, we propose a strategy for generating 2D magnetic AE, which requires two fundamental criteria, i.

Common Defects Accelerate Charge Separation and Reduce Recombination in CNT/Molecule Composites: Atomistic Quantum Dynamics.

Carbon nanotubes (CNTs) are appealing candidates for solar and optoelectronic applications. Traditionally used as electron sinks, CNTs can also perform as electron donors, as exemplified by coupling with perylenediimide (PDI). To achieve high efficiencies, electron transfer (ET) should be fast, while subsequent charge recombination should be slow.

Hydroxyl-Boosted Nitrogen Reduction Reaction: The Essential Role of Surface Hydrogen in Functionalized MXenes.

MXenes, an emerging family of two-dimensional (2D) metal carbides and nitrides, have been demonstrated to be effective nitrogen reduction reaction (NRR) catalysts. So far, most of the theoretical studies toward NRR are based on bare MXenes; however, the structural stabilities are questionable. In this work, we studied the NRR process on several synthesized MXenes (TiC, VC, CrC, ZrC, NbC, MoC, HfC, and TaC) with hydroxyl (OH) termination since the structures are preferred under NRR operating conditions as per Pourbaix stability diagrams.

Self-Consistent Potential Correction for Charged Periodic Systems.

Supercell models are often used to calculate the electronic structure of local deviations from the ideal periodicity in the bulk or on the surface of a crystal or in wires. When the defect or adsorbent is charged, a jellium counter charge is applied to maintain overall neutrality, but the interaction of the artificially repeated charges has to be corrected, both in the total energy and in the one-electron eigenvalues and eigenstates. This becomes paramount in slab or wire calculations, where the jellium counter charge may induce spurious states in the vacuum.

Quantifying Proximity, Confinement, and Interventions in Disease Outbreaks: A Decision Support Framework for Air-Transported Pathogens.

The inability to communicate how infectious diseases are transmitted in human environments has triggered avoidance of interactions during the COVID-19 pandemic. We define a metric, Effective ReBreathed Volume (ERBV), that encapsulates how infectious pathogens, including SARS-CoV-2, transport in air. ERBV separates environmental transport from other factors in the chain of infection, allowing quantitative comparisons among situations.

High-Throughput Screening of Synergistic Transition Metal Dual-Atom Catalysts for Efficient Nitrogen Fixation.

Great enthusiasm in single-atom catalysts (SACs) for the nitrogen reduction reaction (NRR) has been aroused by the discovery of metal-N as a promising catalytic center. However, the poor activity and low selectivity of available SACs are far away from the industrial requirement. Through the first-principles high-throughput screening, we find that Fe-Fe distributed on graphite carbon nitride (Fe/-CN) can manipulate the binding strength of the target reaction species (compromises the ability to adsorb NH and NH), therefore achieving the best NRR performance among 23 transition metal (TM) centers.

Neologisms are epidemic: Modeling the life cycle of neologisms in China 2008-2016.

This paper adopts models from epidemiology to account for the development and decline of neologisms based on internet usage. The research design focuses on the issue of whether a host-driven epidemic model is well-suited to explain human behavior regarding neologisms. We extracted the search frequency data from Google Trends that covers the ninety most influential Chinese neologisms from 2008-2016 and found that the majority of them possess a similar rapidly rising-decaying pattern.

Transition-metal adatoms on 2D-GaAs: a route to chiral magnetic 2D materials by design.

Using relativistic density-functional calculations, we examine the magneto-crystalline anisotropy and exchange properties of transition-metal atoms adsorbed on 2D-GaAs. We show that single Mn and Mo atom (Co and Os) strongly bind on 2D-GaAs, and induce local out-of-plane (in-plane) magnetic anisotropy. When a pair of TM atoms is adsorbed on 2D-GaAs in a close range from each other, magnetisation properties change (become tunable) with respect to concentrations and ordering of the adatoms.