Insight into Facile Ion Diffusion in Resistive Switching Medium toward Low Operating Voltage Memory.

The rapid increase in data storage worldwide demands a substantial amount of energy consumption annually. Studies looking at low power consumption accompanied by high-performance memory are essential for next-generation memory. Here, Graphdiyne oxide (GDYO), characterized by facile resistive switching behavior, is systematically reported toward a low switching voltage memristor. The intrinsic large, homogeneous pore-size structure in GDYO facilitates ion diffusion processes, effectively suppressing the operating voltage. The theoretical approach highlights the remarkably low diffusion energy of the Ag ion (0.11 eV) and oxygen functional group (0.6 eV) within three layers of GDYO. The Ag/GDYO/Au memristor exhibits an ultralow operating voltage of 0.25 V with a GDYO thickness of 5 nm; meanwhile, the thicker GDYO of 29 nm presents multilevel memory with an ON/OFF ratio of up to 104. The findings shed light on memory resistive switching behavior, facilitating future improvements in GDYO-based devices toward opto-memristors, artificial synapses, and neuromorphic applications.

Relationship between Structure and Performance of Atomic-Scale Electrocatalysts for Water Splitting.

Atomic-scale electrocatalysts greatly improve the performance and efficiency of water splitting but require special adjustments of the supporting structures for anchoring and dispersing metal single atoms. Here, the structural evolution of atomic-scale electrocatalysts for water splitting is reviewed based on different synthetic methods and structural properties that create different environments for electrocatalytic activity. The rate-determining step or intermediate state for hydrogen or oxygen evolution reactions is energetically stabilized by the coordination environment to the single-atom active site from the supporting material. In large-scale practical use, maximizing the loading amount of metal single atoms increases the efficiency of the electrocatalyst and reduces the economic cost. Dual-atom electrocatalysts with two different single-atom active sites react with an increased number of water molecules and reduce the adsorption energy of water derived from the difference in electronegativity between the two metal atoms. In particular, single-atom dimers induce asymmetric active sites that promote the degradation of H2 O to H2 or O2 evolution. Consequently, the structural properties of atomic-scale electrocatalysts clarify the atomic interrelation between the catalytic active sites and the supporting material to achieve maximum efficiency.

Nanoparticle Linker-Controlled Molecular Wire Devices Based on Double Molecular Monolayers.

Highly conductive molecular wires are an important component for realizing molecular electronic devices and have to be explored in terms of interactions between molecules and electrodes in their molecular junctions. Here, new molecular wire junctions are reported to enhance charge transport through gold nanoparticle (AuNP)-linked double self-assembled monolayers (SAMs) of cobalt (II) bis-terpyridine molecules (e.g., Co(II)(tpyphS)2 ). Electrical characteristics of the double-SAM devices are explored in terms of the existence of AuNP. The AuNP linker in the Co(II)(tpyphS)2 -AuNP-Co(II)(tpyphS)2 junction acts as an electronic contact that is transparent to electrons. The weak temperature dependency of the AuNP-linked molecular junctions strongly indicates sequential tunneling conduction through the highest occupied molecular orbitals (HOMOs) of Co(II)(tpyphS)2 molecules. The electrochemical characteristics of the AuNP-Co(II)(tpyphS)2 SAMs reveal fast electron transfer through molecules linked by AuNP. Density functional theory calculations reveal that the molecular HOMO levels are dominantly affected by the formation of junctions. The intermolecular charge transport, controlled by the AuNP linker, can provide a rational design for molecular connection that achieves a reliable electrical connectivity of molecular electronic components for construction of molecular electronic circuits.

Functional Molecular Junctions Derived from Double Self-Assembled Monolayers.

Information processing using molecular junctions is becoming more important as devices are miniaturized to the nanoscale. Herein, we report functional molecular junctions derived from double self-assembled monolayers (SAMs) intercalated between soft graphene electrodes. Newly assembled molecular junctions are fabricated by placing a molecular SAM/(top) electrode on another molecular SAM/(bottom) electrode by using a contact-assembly technique. Double SAMs can provide tunneling conjugation across the van der Waals gap between the terminals of each monolayer and exhibit new electrical functions. Robust contact-assembled molecular junctions can act as platforms for the development of equivalent contact molecular junctions between top and bottom electrodes, which can be applied independently to different kinds of molecules to enhance either the structural complexity or the assembly properties of molecules.

Characterization of a novel cold-active esterase isolated from swamp sediment metagenome.

A functional screen of a metagenomic library from "Upo" swamp sediment in Korea identified a gene EstL28, the product of which displayed lipolytic properties on a tributyrin-supplemented medium. The EstL28 sequence encodes a 290 amino acid protein (designated as EstL28), with a predicted molecular weight of 31.3 kDa. The encoded EstL28 protein exhibited the highest sequence similarity (45 %) to a hydrolase found in Streptococcus sanguinis. Phylogenetic analysis indicated that EstL28 belongs to a currently uncharacterized family of esterases. Within the conserved α/ß-hydrolase 6 domain, the EstL28 retains the catalytic triad Ser103-Asp248-His268 that is typical of esterases. The Ser103 residue in the catalytic triad is located in the consensus pentapeptide motif GXSXG. The purified EstL28 enzyme worked optimally at 35 °C and pH 8.5 and remained stable at temperatures lower than 20 °C. The catalytic activity of EstL28 was maximal with p-nitrophenyl butyrate, indicating that it was an esterase. This enzyme also exhibited stable activity in the presence of methanol, ethanol, isopropanol, and dimethyl sulfoxide. Therefore, the level of stability in organic solvents and cold temperature suggests that EstL28 has potential for many biotechnological applications.

Indoor-Light-Activated Blue TiO2-Molecule-WO3 Visible Photocatalyst for Antibacterial Performance against Escherichia coli.

Currently used visible light catalysts either operate with high-power light sources or require prolonged periods of time for catalytic reactions. This presents a limitation regarding facile application in indoor environments and spaces frequented by the public. Furthermore, this gives rise to elevated power consumption. Here, we enhance photocatalytic performance with blue TiO2 and WO3 complexes covalently coupled through an organic molecule, 3-mercaptopropionic acid, under indoor light. Antibacterial experiments against 108 CFU/mL Escherichia coli (E. coli) suspensions were conducted under indoor light exposure conditions. They showed a sterilization effect of almost 90% within 70 min and nearly 100% after 110 min. The complex generates reactive oxygen species (ROS), such as •OH and O2•-, under natural air conditions. We also showed that h+ and •OH are important for sterilizing E. coli using common scavengers. This research highlights the potential of these complexes to generate ROS, effectively playing a crucial role in antibacterial effects under indoor light.

Ultrasensitive Carbon Monoxide Gas Sensor at Room Temperature Using Fluorine-Graphdiyne.

Currently, most carbon monoxide (CO) gas sensors work at high temperatures of over 150 °C. Developing CO gas sensors that operate at room temperature is challenging because of the sensitivity trade-offs. Here, we report an ultrasensitive CO gas sensor at room temperature using fluorine-graphdiyne (F-GDY) in which electrons are increased by light. The GDY films used as channels of field-effect transistors were prepared by using chemical vapor deposition and were characterized by using various spectroscopic techniques. With exposure to UV light, F-GDY showed a more efficient photodoping effect than hydrogen-graphdiyne (H-GDY), resulting in a larger negative shift in the charge neutral point (CNP) to form an n-type semiconductor and an increase in the Fermi level from -5.27 to -5.01 eV. Upon CO exposure, the negatively shifted CNP moved toward a positive shift, and the electrical current decreased, indicating electron transfer from photodoped GDYs to CO. Dynamic sensing experiments demonstrated that negatively charged F-GDY is remarkably sensitive to an electron-deficient CO gas, even with a low concentration of 200 parts per billion. This work provides a promising solution for enhancing the CO sensitivity at room temperature and expanding the application of GDYs in electronic devices.

Low-Temperature Layer-by-Layer Growth of Semiconducting Few-Layer γ-Graphyne to Exploit Robust Biocompatibility.

The sp-hybridized carbon network in single- or few-layer γ-graphyne (γ-GY) has a polarized electron distribution, which can be crucial in overcoming biosafety issues. Here, we report the low-temperature synthesis, electronic properties, and amyloid fibril nanostructures of electrostatic few-layer γ-GY. ABC stacked γ-GY is synthesized by layer-by-layer growth on a catalytic copper surface, exhibiting intrinsic p-type semiconducting properties in few-layer γ-GY. Thickness-dependent electronic properties of γ-GY elucidate interlayer interactions by electron doping between electrostatic layers and layer stacking-involved modulation of the band gap. Electrostatic few-layer γ-GY induces high electronic sensitivity and intense interaction with amyloid beta (i.e., Aß40) peptides assembling into elongated mature Aß40 fibrils. Two-dimensional biocompatible nanostructures of Aß40 fibrils/few-layer γ-GY enable excellent cell viability and high neuronal differentiation of living cells without external stimulation.

Highly Efficient Van Der Waals Heterojunction on Graphdiyne toward the High-Performance Photodetector.

Graphdiyne (GDY), a new 2D material, has recently proven excellent performance in photodetector applications due to its direct bandgap and high mobility. Different from the zero-gap of graphene, these preeminent properties made GDY emerge as a rising star for solving the bottleneck of graphene-based inefficient heterojunction. Herein, a highly effective graphdiyne/molybdenum (GDY/MoS2 ) type-II heterojunction in a charge separation is reported toward a high-performance photodetector. Characterized by robust electron repulsion of alkyne-rich skeleton, the GDY based junction facilitates the effective electron-hole pairs separation and transfer. This results in significant suppression of Auger recombination up to six times at the GDY/MoS2 interface compared with the pristine materials owing to an ultrafast hot hole transfer from MoS2 to GDY. GDY/MoS2 device demonstrates notable photovoltaic behavior with a short-circuit current of -1.3 × 10-5 A and a large open-circuit voltage of 0.23 V under visible irradiation. As a positive-charge-attracting magnet, under illumination, alkyne-rich framework induces positive photogating effect on the neighboring MoS2 , further enhancing photocurrent. Consequently, the device exhibits broadband detection (453-1064 nm) with a maximum responsivity of 78.5 A W-1 and a high speed of 50 µs. Results open up a new promising strategy using GDY toward effective junction for future optoelectronic applications.

Atomic dopants involved in the structural evolution of thermally graphitized graphene.

Thermally doped nitrogen atoms on the sp(2)-carbon network of reduced graphene oxide (rGO) enhance its electrical conductivity. Atomic structural information of thermally annealed graphene oxide (GO) provides an understanding on how the heteroatomic doping could affect electronic property of rGO. Herein, the spectroscopic and microscopic variations during thermal graphitization from 573 to 1,373 K are reported in two different rGO sheets, prepared by thermal annealing of GO (rGO(therm)) and post-thermal annealing of chemically nitrogen-doped rGO (post-therm-rGO(N(2)H(4))). The spectroscopic transitions of rGO(N(2)H(4)) in thermal annealing ultimately showed new oxygen-functional groups, such as cyclic edge ethers and new graphitized nitrogen atoms at 1,373 K. During the graphitization process, the microscopic evolution resolved by scanning tunneling microscopy (STM) produced more wrinkled surface morphology with graphitized nanocrystalline domains due to atomic doping of nitrogen on a post-therm-rGO(N(2)H(4)) sheet. As a result, the post-therm-rGO(N(2)H(4))-containing nitrogen showed a less defected sp(2)-carbon network, resulting in enhanced conductivity, whereas the rGO(therm) sheet containing no nitrogen had large topological defects on the basal plane of the sp(2)-carbon network. Thus, our investigation of the structural evolution of original wrinkles on a GO sheet incorporated into the graphitized N-doped rGO helps to explain how the atomic doping can enhance the electrical conductivity.

Can commonly used hydrazine produce n-type graphene?

A simple chemical method to obtain bulk quantities of N-doped, reduced graphene oxide (rGO) sheets (see figure) as an n-type semiconductor through the treatment of as-prepared GO sheets with the commonly used reducing reagent hydrazine, followed by rapid thermal annealing (RTA) is described.

Electrochemical nanoscale templating: laterally self-aligned growth of organic-metal nanostructures.

The electrodeposition of Ag into organized surfactant templates adsorbed onto (22 × âˆš3) reconstructed Au(111) is investigated by in situ electrochemical scanning tunneling microscopy. Ag(+) concentrations of as low as 2.5 × 10(-6) M allow the visualization of the electrochemical molecular templating effect of a sodium dodecyl sulfate (SDS) adlayer. The SDS hemicylindrical stripes determine the adsorption sites of the Ag(+) ions and the directionality of Ag nanodeposition. The SDS-Ag nanostructures grow along the long axis of SDS hemicylindrical stripes, and an interaction of Ag with the Au(111) substrate leads to a structural change in the SDS stripe pattern. The SDS-Ag nanostructures undergo dynamic rearrangement in response to changes in the applied electrode potential. At negative potentials, the orientations of SDS-Ag nanostructures are pinned by the (22 × âˆš3) reconstructed pattern. Furthermore, observed differences in Ag nanostructuring on Au(111) without molecular templates (i.e., on a bare Au(111) surface) confirm the role of self-assembled organic templates in producing metal-organic nanostructures under control of the surface potential, which can determine the feature size, shape, and period of the metal nanostructure arrays.

CNT-molecule-CNT (1D-0D-1D) van der Waals integration ferroelectric memory with 1-nm2 junction area.

The device's integration of molecular electronics is limited regarding the large-scale fabrication of gap electrodes on a molecular scale. The van der Waals integration (vdWI) of a vertically aligned molecular layer (0D) with 2D or 3D electrodes indicates the possibility of device's integration; however, the active junction area of 0D-2D and 0D-3D vdWIs remains at a microscale size. Here, we introduce the robust fabrication of a vertical 1D-0D-1D vdWI device with the ultra-small junction area of 1 nm2 achieved by cross-stacking top carbon nanotubes (CNTs) on molecularly assembled bottom CNTs. 1D-0D-1D vdWI memories are demonstrated through ferroelectric switching of azobenzene molecules owing to the cis-trans transformation combined with the permanent dipole moment of the end-tail -CF3 group. In this work, our 1D-0D-1D vdWI memory exhibits a retention performance above 2000 s, over 300 cycles with an on/off ratio of approximately 105 and record current density (3.4 × 108 A/cm2), which is 100 times higher than previous study through the smallest junction area achieved in a vdWI. The simple stacking of aligned CNTs (4 × 4) allows integration of memory arrays (16 junctions) with high device operational yield (100%), offering integration guidelines for future molecular electronics.

Inductive Effect of Lewis Acidic Dopants on the Band Levels of Perovskite for a Photocatalytic Reaction.

Band-edge modulation of halide perovskites as photoabsorbers plays significant roles in the application of photovoltaic and photochemical systems. Here, Lewis acidity of dopants (M) as the new descriptor of engineering the band-edge position of the perovskite is investigated in the gradiently doped perovskite along the core-to-surface (CsPbBr3-CsPb1-xMxBr3). Reducing M-bromide bond strength with an increase in hardness of acidic M increases the electron ability of basic Br, thus strengthening the Pb-Br orbital coupling in M-Pb-Br, noted as the inductive effect of dopants. Especially, the highly hard Lewis acidic Mg localized in the outer position of the perovskite induces the increase of work function and then shifts band edge upward along the core-to-surface of the perovskite. Thus, charge separation driven by the dopant-induced internal electric field induces the slow annihilation of the excited holes, improving the slow aromatic Csp3-H dissociation in the photocatalytic oxidation process by ∼211% (491.39 µmol g-1 h-1) enhancements, compared with undoped nanocrystals.

Unveiling surface charge on chalcogen atoms toward the high aspect-ratio colloidal growth of two-dimensional transition metal chalcogenides.

Controlling surface energies of each facet is essential for the anisotropic growth of two-dimensional transition metal chalcogenides (TMCs). However, it is a challenge due to stronger binding energies of ligand head groups to the edge facets compared to the planar facets. Herein, we demonstrate that the adsorption of ligands on metal positions can induce partial electron localization on the chalcogen sites, and then accelerate metal-chalcogen bond formation for enhanced anisotropic growth of nanosheets. And only in the case of trioctylphosphine oxide (TOPO)-adsorbed nanosheets, surface polarization can be unveiled on the surface of the colloidal nanosheets due to restricted development of nonpolar ligand shells by the steric effects of the ligands. Moreover, density functional theory (DFT) calculation results reveal that the decrease of surface energy on the (100) edge facets as well as the increase on the (001) basal facets by the adsorption of triorganylphosphine oxide also contribute to the preferentially lateral growth. As a result, various 2D TMCs, including MoSe2, WSe2, and SnSe2 synthesized with TOPO, show enhanced anisotropic growth.

Uncovering the Role of Countercations in Ligand Exchange of WSe2: Tuning the d-Band Center toward Improved Hydrogen Desorption.

The role of countercations that do not bind to core nanocrystals (NCs) but rather ensure charge balance on ligand-exchanged NC surfaces has been rarely studied and even neglected. Such a scenario is unfortunate, as an understanding of surface chemistry has emerged as a key factor in overcoming colloidal NC limitations as catalysts. In this work, we report on the unprecedented role of countercations in ligand exchange for a colloidal transition metal dichalcogenide (TMD), WSe2, to tune the d-band center toward the Fermi level for enhanced hydrogen desorption. Conventional long-chain organic ligands, oleylamine, of WSe2 NCs are exchanged with short atomic S2- ligands having countercations to preserve the charge balance (WSe2/S2-/M+, M = Li, Na, K). Upon exchange with S2- ligands, the charge-balancing countercations are intercalated between WSe2 layers, thereby serving a unique function as an electrochemical hydrogen evolution reaction (HER) catalyst. The HER activity of ligand-exchanged colloidal WSe2 NCs shows a decrease in overpotential by down-shift of d-band center to induce more electron-filling in antibonding orbital and an increase in the electrochemical active surface area (ECSA). Exchanging surface functionalities with S2- anionic ligands enhances HER kinetics, while the existence of intercalated countercations improves charge transfer with the electrolyte. The obtained results suggest that both anionic ligands and countercationic species in ligand exchange must be considered to enhance the overall catalytic activity of colloidal TMDs.

Efficient and Stable Solar Hydrogen Generation of Hydrophilic Rhenium-Disulfide-Based Photocatalysts via Chemically Controlled Charge Transfer Paths.

Effective charge separation and rapid transport of photogenerated charge carriers without self-oxidation in transition metal dichalcogenide photocatalysts are required for highly efficient and stable hydrogen generation. Here, we report that a molecular junction as an electron transfer path toward two-dimensional rhenium disulfide (2D ReS2) nanosheets from zero-dimensional titanium dioxide (0D TiO2) nanoparticles induces high efficiency and stability of solar hydrogen generation by balanced charge transport of photogenerated charge carriers. The molecular junctions are created through the chemical bonds between the functionalized ReS2 nanosheets (e.g., -COOH groups) and -OH groups of two-phase TiO2 (i.e., ReS2-C6H5C(═O)-O-TiO2 denoted by ReS2-BzO-TiO2). This enhances the chemical energy at the conduction band minimum of ReS2 in ReS2-BzO-TiO2, leading to efficiently improved hydrogen reduction. Through the molecular junction (a Z-scheme charge transfer path) in ReS2-BzO-TiO2, recombination of photogenerated charges and self-oxidation of the photocatalyst are restrained, resulting in a high photocatalytic activity (9.5 mmol h-1 per gram of ReS2 nanosheets, a 4750-fold enhancement compared to bulk ReS2) toward solar hydrogen generation with high cycling stability of more than 20 h. Our results provide an effective charge transfer path of photocatalytic TMDs by preventing self-oxidation, leading to increases in photocatalytic durability and a transport rate of the photogenerated charge carriers.