Instantaneous Thermal Energy for Swift Synthesis of Single-Atom Catalysts for Unparalleled Performance in Metal-Air Batteries and Fuel Cells.

Based on experimental and computational evidence, phthalocyanine (Pc) compounds in the form of quaternary-bound metal-nitrogen (N) atoms are the most effective catalysts for oxygen reduction reaction (ORR). However, the heat treatment process used in their synthesis may compromise the ideal structure, causing the agglomeration of transition metals. To overcome this issue, a novel method is developed for synthesizing iron (Fe) single-atom catalysts with ideal structures supported by thermally exfoliated graphene oxide (GO). This is achieved through a short heat treatment of only 2.5 min involving FePc and N, N-dimethylformamide in the presence of GO. According to the synthesis mechanism revealed by this study, carbon monoxide acts as a strong linker between the single Fe atoms and graphene. It facilitates the formation of a structure containing oxygen species between FeN4 and graphene, which provides high activity and stability for the ORR. These catalysts possess an enormous number of active sites and exhibit enhanced activity toward the alkaline ORR. They demonstrate excellent performance when applied to real electrochemical devices, such as zinc-air batteries and anion exchange membrane fuel cells. It is expected that the instantaneous heat treatment method developed in this study will aid in the development of high-performing single-atom catalysts.

High-Power and Large-Area Anodes for Safe Lithium-Metal Batteries.

The lithium deposited via the complex electrochemical heterogeneous lithium deposition reaction (LDR) process on a lithium foil-based anode (LFA) forms a high-aspect-ratio shape whenever the reaction kinetics reach its limit, threatening battery safety. Thereby, a research strategy that boosts the LDR kinetics is needed to construct a high-power and safe lithium metal anode. In this study, the kinetic limitations of the LDR process on LFA are elucidated through operando and ex situ observations using in-depth electrochemical analyses. In addition, ultra-thin (≈0.5 µm) and high modulus (≥19 GPa) double-walled carbon nanotube (DWNT) membranes with different surface properties are designed to catalyze high-safety LDRs. The oxygen-functionalized DWNT membranes introduced on the LFA top surface simultaneously induce multitudinous lithium nuclei, leading to film-like lithium deposition even at a high current density of 20 mA cm-2. More importantly, the layer-by-layer assembly of the oxygen-functionalized and pristine DWNT membranes results in different surface energies between the top and bottom surfaces, enabling selective surface LDRs underneath the high-modulus bilayer membranes. The protective LDR on the bilayer-covered LFA guarantees an invulnerable cycling process in large-area pouch cells at high current densities for more than 1000 cycles, demonstrating the practicability of LFA in a conventional liquid electrolyte system.

Iridium-Cooperated, Symmetry-Broken Manganese Oxide Nanocatalyst for Water Oxidation.

The water oxidation reaction, the most important reaction for hydrogen production and other sustainable chemistry, is efficiently catalyzed by the Mn4CaO5 cluster in biological photosystem II. However, synthetic Mn-based heterogeneous electrocatalysts exhibit inferior catalytic activity at neutral pH under mild conditions. Symmetry-broken Mn atoms and their cooperative mechanism through efficient oxidative charge accumulation in biological clusters are important lessons but synthesis strategies for heterogeneous electrocatalysts have not been successfully developed. Here, we report a crystallographically distorted Mn-oxide nanocatalyst, in which Ir atoms break the space group symmetry from I41/amd to P1. Tetrahedral Mn(II) in spinel is partially replaced by Ir, surprisingly resulting in an unprecedented crystal structure. We analyzed the distorted crystal structure of manganese oxide using TEM and investigated how the charge accumulation of Mn atoms is facilitated by the presence of a small amount of Ir.

Energy Landscapes for Lithium Incorporation and Diffusion in Multidomain Silicon Suboxide Anode Materials.

In-depth understanding of the lithium interaction characteristics within multidomain silicon suboxide is indispensable for optimizing the electrochemical performance of silicon suboxide anode materials for lithium-ion batteries. In this study, we investigate the domain-dependent thermodynamic and kinetic properties of lithium atoms within systematically designed multidomain silicon suboxide models composed of Si, SiO2, and Si/SiO2 interface by performing a series of computational simulations combined with a unique tomography-like sampling scheme. We find that the Si/SiO2 interfacial region exhibits preferential thermodynamics and kinetics for lithiation and can serve as a critical lithium transport channel during charge-discharge cycles, while the SiO2 domain is likely to be excluded from lithiation due to its high resistance to lithium diffusion. Consequently, a significant fraction of lithium is expected to be trapped at the Si/SiO2 interface during the discharge process, which ultimately contributes to a low initial Coulombic efficiency. This theoretical understanding suggests that the formation of continuously connected lithium-transportable Si/SiO2 interfacial channels surrounding the Si domains, along with a well-structured shallow SiO2 framework through the use of appropriate synthesis methods, is essential for maximizing the electrochemical performance of silicon suboxide anode materials.

Revisiting Lithium- and Sodium-Ion Storage in Hard Carbon Anodes.

The galvanostatic lithiation/sodiation voltage profiles of hard carbon anodes are simple, with a sloping drop followed by a plateau. However, a precise understanding of the corresponding redox sites and storage mechanisms is still elusive, which hinders further development in commercial applications. Here, a comprehensive comparison of the lithium- and sodium-ion storage behaviors of hard carbon is conducted, yielding the following key findings: 1) the sloping voltage section is presented by the lithium-ion intercalation in the graphitic lattices of hard carbons, whereas it mainly arises from the chemisorption of sodium ions on their inner surfaces constituting closed pores, even if the graphitic lattices are unoccupied; 2) the redox sites for the plateau capacities are the same as those for the closed pores regardless of the alkali ions; 3) the sodiation plateau capacities are mostly determined by the volume of the available closed pore, whereas the lithiation plateau capacities are primarily affected by the intercalation propensity; and 4) the intercalation preference and the plateau capacity have an inverse correlation. These findings from extensive characterizations and theoretical investigations provide a relatively clear elucidation of the electrochemical footprint of hard carbon anodes in relation to the redox mechanisms and storage sites for lithium and sodium ions, thereby providing a more rational design strategy for constructing better hard carbon anodes.

On the importance of the electric double layer structure in aqueous electrocatalysis.

To design electrochemical interfaces for efficient electric-chemical energy interconversion, it is critical to reveal the electric double layer (EDL) structure and relate it with electrochemical activity; nonetheless, this has been a long-standing challenge. Of particular, no molecular-level theories have fully explained the characteristic two peaks arising in the potential-dependence of the EDL capacitance, which is sensitively dependent on the EDL structure. We herein demonstrate that our first-principles-based molecular simulation reproduces the experimental capacitance peaks. The origin of two peaks emerging at anodic and cathodic potentials is unveiled to be an electrosorption of ions and a structural phase transition, respectively. We further find a cation complexation gradually modifies the EDL structure and the field strength, which linearly scales the carbon dioxide reduction activity. This study deciphers the complex structural response of the EDL and highlights its catalytic importance, which bridges the mechanistic gap between the EDL structure and electrocatalysis.

Sodium-Doped Titania Self-Rectifying Memristors for Crossbar Array Neuromorphic Architectures.

Memristors integrated into a crossbar-array architecture (CAA) are promising candidates for nonvolatile memory elements in artificial neural networks. However, the relatively low reliability of memristors coupled with crosstalk and sneak currents in CAAs have limited the realization of the full potential of this technology. Here, high-reliability Na-doped TiO2  memristors grown in situ by atomic layer deposition (ALD) are demonstrated, where reversible Na migration underlies the resistive-switching mechanism. By employing ALD growth with an aqueous NaOH reactant in deionized water, uniform implantation of Na dopants is achieved in the crystallized TiO2  thin films at 250 °C without post-annealing. The resulting Na-doped TiO2  memristors show electroforming-free and self-rectifying resistive-switching behavior, and they are ideally suited for selectorless CAAs. Effective addressing of selectorless nodes is demonstrated via electrical measurement of individual memristors in a 6 × 6 crossbar using a read current of less than 1 µA with negligible sneak current at or below the noise level of ≈100 pA. Finally, the long-term potentiation and depression synaptic behavior from these Na-doped TiO2  memristors achieves greater than 99.1% accuracy for image-recognition tasks using a convolutional neural network based on the selectorless of crossbar arrays.

Understanding the Effects of Interfacial Lithium Ion Concentration on Lithium Metal Anode.

Despite the development of multidimensional state-of-the-art electrode materials for constructing better lithium metal anodes (LMAs), the key factors influencing the electrochemical performance of LMAs are still poorly understood. Herein, it is demonstrated that the local lithium ion concentration at the interface between the electrode and electrolyte exerts significant influence on the electrochemical performance of LMAs. The local ion concentration is multiplied by introducing pseudocapacitive nanocarbons (PNCs) containing numerous heteroatoms, because PNCs can store large numbers of lithium ions in a pseudocapacitive manner, and promote the formation of an electrochemical double layer. The high interfacial lithium ion concentration induces the formation of lithium-rich inorganic solid-electrolyte-interface layers with high ionic conductivities, and facilitates sustainable and stable supplies of lithium ion charge carriers on the overall active surfaces of the PNCs. Accordingly, the PNC-induced LMA exhibits high Coulombic efficiencies, high rate capabilities, and stable cycling performance.

Flash Bottom-Up Arc Synthesis of Nanocarbons as a Universal Route for Fabricating Single-Atom Electrocatalysts.

Despite considerable development in the field of single-atom catalysts (SACs) on carbon-based materials, the reported strategies for synthesizing SACs generally rely on top-down approaches, which hinder achieving both simple and universal synthesis routes that are simultaneously applicable to various metals and nanocarbons. Here, a universal strategy for fabricating nanocarbon based-SACs using a flash bottom-up arc discharge method to mitigate these issues is reported. The ionization of elements and their recombination process during arc discharge allows the simultaneous incorporation of single metal atoms (Mn, Fe, Co, Ni, and Pt) into the crystalline carbon lattice during the formation of carbon nanohorns (CNHs) and N-doped arc graphene. The coordination environment around the Co atoms of Co1 /CNH can be modulated by a mild post-treatment with NH3 . As a result, Co1 /CNH exhibits good oxygen reduction reaction activity, showing a 1.92 times higher kinetic current density value than the commercial Pt/C catalyst in alkaline media. In a single cell experiment, Co1 /CNH exhibits the highest maximum power density of 472 mW cm-2 compared to previously reported nonprecious metal-based SACs.

Crystal Phase Transition Creates a Highly Active and Stable RuCX Nanosurface for Hydrogen Evolution Reaction in Alkaline Media.

Although metastable crystal structures have received much attention owing to their utilization in various fields, their phase-transition to a thermodynamic structure has attracted comparably little interest. In the case of nanoscale crystals, such an exothermic phase-transition releases high energy within a confined surface area and reconstructs surface atomic arrangement in a short time. Thus, this high-energy nanosurface may create novel crystal structures when some elements are supplied. In this work, the creation of a ruthenium carbide (RuCX , X < 1) phase on the surface of the Ru nanocrystal is discovered during phase-transition from cubic-close-packed to hexagonal-close-packed structure. When the electrocatalytic hydrogen evolution reaction (HER) is tested in alkaline media, the RuCX exhibits a much lower overpotential and good stability relative to the counterpart Ru-based catalysts and the state-of-the-art Pt/C catalyst. Density functional theory calculations predict that the local heterogeneity of the outermost RuCX surface promotes the bifunctional HER mechanism by providing catalytic sites for both H adsorption and facile water dissociation.

Spectroscopic capture of a low-spin Mn(IV)-oxo species in Ni-Mn3O4 nanoparticles during water oxidation catalysis.

High-valent metal-oxo moieties have been implicated as key intermediates preceding various oxidation processes. The critical O-O bond formation step in the Kok cycle that is presumed to generate molecular oxygen occurs through the high-valent Mn-oxo species of the water oxidation complex, i.e., the Mn4Ca cluster in photosystem II. Here, we report the spectroscopic characterization of new intermediates during the water oxidation reaction of manganese-based heterogeneous catalysts and assign them as low-spin Mn(IV)-oxo species. Recently, the effects of the spin state in transition metal catalysts on catalytic reactivity have been intensely studied; however, no detailed characterization of a low-spin Mn(IV)-oxo intermediate species currently exists. We demonstrate that a low-spin configuration of Mn(IV), S = 1/2, is stably present in a heterogeneous electrocatalyst of Ni-doped monodisperse 10-nm Mn3O4 nanoparticles via oxo-ligand field engineering. An unprecedented signal (g = 1.83) is found to evolve in the electron paramagnetic resonance spectrum during the stepwise transition from the Jahn-Teller-distorted Mn(III). In-situ Raman analysis directly provides the evidence for Mn(IV)-oxo species as the active intermediate species. Computational analysis confirmed that the substituted nickel species induces the formation of a z-axis-compressed octahedral C4v crystal field that stabilizes the low-spin Mn(IV)-oxo intermediates.

Single-and repeat-dose toxicity of HM10760A, a long-acting erythropoietin, in rats and monkeys.

Anemia is a frequent complication of chronic kidney disease (CKD) that causes an increase in morbidity and mortality and accelerates the rate of disease progression. Treatment with recombinant human erythropoietin (rhEPO) is a major breakthrough in the therapy of renal anemia. HM10760A, a long-acting EPO, has been developed as a treatment for anemia in CKD patients. A series of preclinical toxicology studies, such as acute, 4 week repeat-dose, and 13 week repeat-dose, was completed to support the safety of human exposure to HM10760A for up to 13 weeks. The rodent and non-rodent species used in the pivotal preclinical general toxicity studies were rats and monkeys, respectively. A once-a-week or once-every-two-week i.v dosing regimen was applied for 4 week and 13 week repeat-dose toxicity studies, respectively, in consideration of the expected administration frequency in humans. Based on the 13 week repeat-dose toxicity studies, 2.61 µg/kg and 22.03 µg/kg can be considered as the NOAELs (no observed adverse effect levels) in rats and monkeys, respectively. Almost all observations recorded at the low- and mid-dose levels are typical pharmacological effects of EPO and not uniquely attributed HM10760A toxicity. To account for the differences between human being and animal physiologies, the safety of HM10760A needs to be further confirmed in future clinical studies.

Designed growth of porous 2D Nb2O5 with Ag nano-particles for differential detection of UV-A and UV-C.

We demonstrate the differential detection of UV-A (ultra-violet 320-400 nm region) and UV-C (100-280 nm) using porous two-dimensional (2D) Nb2O5 and additional Ag nano-particle decoration. The 2D Nb2O5, which has band-absorption edge near the UV-A zone, was synthesized by thermodynamic conversion of 2D material NbSe2 (Nb2O5 has lower Gibbs formation energy than NbSe2). For the differential detection (to distinguish with UV-C absorption), we decorated the Ag nano-particles on the Nb2O5 surface. By coating Ag nano-particles, we can expect (i) a decrease in the area of light absorption by the Ag-coated area, and (ii) an increase of surface plasmon absorption by Ag nano-particles, especially the UV-A region, resulting in strong intensity ratio change UV-A/UV-C.

Multiple Transfer of Layer-by-Layer Nanofunctional Films by Adhesion Controls.

Transfer methods to displace active functional layers onto desired surfaces have been developed for the fabrication of nanostructured thin film devices. However, multiple transfers with highly polar surfaces were not yet fully demonstrated presumably due to difficulty in the control of the competitive adhesions at interfaces. In this study, we present adhesion-assisted multiple transfer methods for the fabrication of highly ordered nanolaminated structures with layer-by-layer (LbL) assembled films composed of various functional nanomaterials. The interfacial adhesions were controlled with adhesive layers having a thickness of only 2.5 nm for the successful transfer of the LbL nanofunctional films from the donor substrates to the receiver substrates, which was determined mainly by the major functional moieties at the contact surfaces. The root-mean-square roughness should be lower than 200 nm for conformal contact in the transfer. The versatility of the proposed method was demonstrated with various functional Au, silica, ZnO, and TiO2 nanoparticles as constituent materials and various types of substrates including Si wafer, glass, and polyethylene terephthalate surfaces. The fabricated films with periodic depositions of two different materials could exhibit photoreflective properties with high-order reflection peaks, which were simply tunable by adjusting the order in the multiple transfer. This transfer method could effectively reduce the cost and time in the nanofabrication as it did not require costly equipment, harsh synthesis conditions, and hazardous solvents.

Theoretical and Experimental Understanding of Hydrogen Evolution Reaction Kinetics in Alkaline Electrolytes with Pt-Based Core-Shell Nanocrystals.

The free energy of H adsorption (ΔGH) on a metallic catalyst has been taken as a descriptor to predict the hydrogen evolution reaction (HER) kinetics but has not been well applied in alkaline media. To assess this, we prepare Pd@Pt and PdH@Pt core-shell octahedra enclosed by Pt(111) facets as model catalysts for controlling the ΔGH affected by the ligand, the strain, and their ensemble effects. The Pt shell thickness is adjusted from 1 to 5 atomic layers by varying the amount of Pt precursor added during synthesis. In an alkaline electrolyte, the HER activity of core-shell models is improved either by the construction of core-shell structures or by the increased number of Pt shells. These experimental results are in good agreement with the ΔGH values calculated by the first-principles density functional theory with a complex surface strained core-shell slab model. However, enhanced HER activities of Pd@Pt and PdH@Pt core-shell nanocrystals over the Pt catalyst are inconsistent with the thermodynamic ΔGH scaling relationship only but can be explained by the work function and apparent ΔGH models that predict the interfacial electric field for the HER.

Structure, Dynamics, and Wettability of Water at Metal Interfaces.

The water/metal interface often governs important chemophysical processes in various technologies. Therefore, from scientific and engineering perspectives, the detailed molecular-level elucidation of the water/metal interface is of high priority, but the related research is limited. In experiments, the surface-science techniques, which can provide full structural details of the surface, are not easy to directly apply to the interfacial systems under ambient conditions, and the well-defined facets cannot be entirely free from contamination at the contact with water. To answer long-standing debates regarding the wettability, structure, and dynamics of water at metal interfaces, we here develop reliable first-principles-based multiscale simulations. Using the state-of-the-art simulations, we find that the clean metal surfaces are actually superhydrophilic and yield zero contact angles. Furthermore, we disclose an inadequacy of widespread ice-like bilayer model of the water adlayers on metal surfaces from both averaged structural and dynamic points of view. Our findings on the nature of water on metal surfaces provide new molecular level perspectives on the tuning and design of water/metal interfaces that are at the heart of many energy applications.

Thickness-Dependence Electrical Characterization of the One-Dimensional van der Waals TaSe3 Crystal.

Needle-like single crystalline wires of TaSe3 were massively synthesized using the chemical vapor transport method. Since the wedged-shaped single TaSe3 molecular chains were stacked along the b-axis by weak van der Waals interactions, a few layers of TaSe3 flakes could be easily isolated using a typical mechanical exfoliation method. The exfoliated TaSe3 flakes had an anisotropic planar structure, and the number of layers could be controlled by a repeated peeling process until a monolayer of TaSe3 nanoribbon was obtained. Through atomic force and scanning Kelvin probe microscope analyses, it was found that the variation in the work function with the thickness of the TaSe3 flakes was due to the interlayer screening effect. We believe that our results will not only help to add a novel quasi-1D block for nanoelectronics devices based on 2D van der Waals heterostructures, but also provide crucial information for designing proper contacts in device architecture.

Direct cation exchange of CdSe nanocrystals into ZnSe enabled by controlled binding between guest cations and organic ligands.

Zn chalcogenides are suitable candidates for blue-emitting fluorophores in light-emitting devices. In particular, the efforts to grow ZnSe nanocrystals (NCs) with fine control over size and shape via bottom-up approaches have faced challenges because of the slow decomposition of Zn precursors. In this study, we report direct cation exchange from CdSe NCs to ZnSe. Absorption spectroscopy and density functional theory (DFT) analysis reveal that the reactivity of cation exchange depends on the degree of complexation between organic ligands and Zn halides. We controlled the binding strength of Zn complexes by changing the organic ligands and halogen species that bind with Zn. Appropriate binding strength allows for the release of Zn ions and their facile incorporation into CdSe seed NCs. Under our experimental conditions, trioctylphosphine oxide (TOPO)-ZnI2 drives the efficient cation exchange reaction whereas TOPO-ZnCl2 induces no cation exchange of CdSe NCs. In addition, functional groups vary the binding strength between Zn and ligands. Oleylamine (OLAm)-ZnI2, which has a weaker ligand-ZnI2 binding than TOPO-ZnI2, breaks down the original morphologies of host CdSe NCs due to the very fast exchange rate. On the other hand, the TOPO-ZnI2 complex induces a mild exchange rate, leading to transformation into various morphologies such as CdSe nanorods (NRs) and nanoplatelets (NPLs) into CdSe/ZnSe heterostructures inaccessible via other synthesis methods. The incorporation of Zn into various morphologies of CdSe results in tunable optical transitions in blue-UV regions. The synthesis of heterostructured NCs in an elongated morphology is possible, opening opportunities in photocatalysis, light emitting diodes, and luminescent solar concentrators.

Ultrafast charge transfer coupled with lattice phonons in two-dimensional covalent organic frameworks.

Covalent organic frameworks (COFs) have emerged as a promising light-harvesting module for artificial photosynthesis and photovoltaics. For efficient generation of free charge carriers, the donor-acceptor (D-A) conjugation has been adopted for two-dimensional (2D) COFs recently. In the 2D D-A COFs, photoexcitation would generate a polaron pair, which is a precursor to free charge carriers and has lower binding energy than an exciton. Although the character of the primary excitation species is a key factor in determining optoelectronic properties of a material, excited-state dynamics leading to the creation of a polaron pair have not been investigated yet. Here, we investigate the dynamics of photogenerated charge carriers in 2D D-A COFs by combining femtosecond optical spectroscopy and non-adiabatic molecular dynamics simulation. From this investigation, we elucidate that the polaron pair is formed through ultrafast intra-layer hole transfer coupled with coherent vibrations of the 2D lattice, suggesting a mechanism of phonon-assisted charge transfer.

Enthalpy-Entropy Interplay in π-Stacking Interaction of Benzene Dimer in Water.

Aromatic groups can engage in an interesting class of noncovalent interactions termed π-π interactions, which play a pivotal role in stabilizing a variety of molecular architectures, including nucleic acids, proteins, and supramolecular assemblies. When the aromatic compounds interact with each other in an aqueous environment, their association is facilitated by the hydrophobic effect-the trend of nonpolar solutes to aggregate in a polar solution. To develop an in-depth understanding of hydrophobic association, we investigate in the present work π-π interactions in water, employing as a paradigm the benzene dimer. Using DFT-CES, a mean-field QM/MM method recently developed by our group, we describe the benzene solute at a quantum-mechanical level. Full consideration of detailed solute-electron density enables an optimal description of the solute-solvent interactions, leading to an accurate prediction of hydration free energies. In π-stacking of benzene, we find an entropic stabilization associated with the shrinkage of the solvent-excluded volume, which agrees with the theory of hydrophobic effect at subnanoscales. However, at the equilibrium binding distance of the benzene dimer, we find that the entropic stabilization nearly cancels out due to the enthalpic cost required for dewetting the internal space. Such an enthalpy-entropy compensation leads the association free energy to be predominantly dictated by the solute-solute interaction enthalpy. The present work offers new insight into the mechanistic role of water and the primary thermodynamic driving force of hydrophobic association.