Reconfigurable Resistive Switching Memory for Telegraph Code Sensing and Recognizing Reservoir Computing Systems.

Reservoir computing (RC) system is based upon the reservoir layer, which non-linearly transforms input signals into high-dimensional states, facilitating simple training in the readout layer-a linear neural network. These layers require different types of devices-the former demonstrated as diffusive memristors and the latter prepared as drift memristors. The integration of these components can increase the structural complexity of RC system. Here, a reconfigurable resistive switching memory (RSM) capable of implementing both diffusive and drift dynamics is demonstrated. This reconfigurability is achieved by preparing a medium with a 3D ion transport channel (ITC), enabling precise control of the metal filament that determines memristor operation. The 3D ITC-RSM operates in a volatile threshold switching (TS) mode under a weak electric field and exhibits short-term dynamics that are confirmed to be applicable as reservoir elements in RC systems. Meanwhile, the 3D ITC-RSM operates in a non-volatile bipolar switching (BS) mode under a strong electric field, and the conductance modulation metrics forming the basis of synaptic weight update are validated, which can be utilized as readout elements in the readout layer. Finally, an RC system is designed for the application of reconfigurable 3D ITC-RSM, and performs real-time recognition on Morse code datasets.

Atomistic Scale Modeling of Anode/Electrolyte Interfaces in Li-Ion Batteries.

A key issue in lithium-ion batteries is understanding the solid electrolyte interphase (SEI) resulting from a reductive reaction on the anode/electrolyte interface. The presence of the SEI layer affects the transport behavior of the ions and electrons between the anode and electrolyte. Despite the influence on interfacial properties, the formation and evolution mechanism of the SEI layer are unclear owing to their complexity and dynamic nature. Atomistic-scale simulations have promoted the understanding of the reaction mechanism on the anode/electrolyte interface, the formation and evolution of the SEI layer, and their fundamental properties. This Perspective discusses the modeling and interpretations of anode/SEI/electrolyte interfaces through computational methods at the atomic-scale and highlights interfacial modeling techniques for a realistic interface design, which can overcome the limited time and length scale with high accuracy.

Probing One-Dimensional Oxygen Vacancy Channels Driven by Cation-Anion Double Ordering in Perovskites.

Visualizing the oxygen vacancy distributions is highly desirable for understanding the atomistic oxygen diffusion mechanisms in perovskites. In particular, the direct observation of the one-dimensional oxygen vacancy channels has not yet been achieved in perovskites with dual ion (i.e., cation and anion) ordering. Here, we perform atomic-resolution imaging of the one-dimensional oxygen vacancy channels and their structural dynamics in a NdBaCo2O5.5 double perovskite oxide. An in situ heating transmission electron microscopy investigation reveals the disordering of oxygen vacancy channels by local rearrangement of oxygen vacancies at the specific temperature. A density functional theory calculation suggests that the possible pathway of oxygen vacancy migration is a multistep route via Co-O and Nd-Ov (oxygen vacancy) sites. These findings could provide robust guidance for understanding the static and dynamic behaviors of oxygen vacancies in perovskite oxides.

Enhancing Thermocatalytic Activities by Upshifting the d-Band Center of Exsolved Co-Ni-Fe Ternary Alloy Nanoparticles for the Dry Reforming of Methane.

Dry reforming of methane (DRM) is a feasible solution to address the reduction of greenhouse gases stipulated by the Paris Climate Agreement, given that it adds value by converting trivial gases, CO2 and CH4 , simultaneously into useful syngas. However, the conventional Ni catalyst undergoes deactivation due to carbon coking and particle agglomeration. Here we demonstrate a highly efficient and durable DRM catalyst: exsolved Co-Ni-Fe ternary alloy nanoparticles on the layered perovskite PrBaMn1.7 Co0.1 Ni0.2 O5+δ produced by topotactic exsolution. This method readily allows the generation of a larger number of exsolved nanoparticles with enhanced catalytic activity above that of Ni monometallic and Co-Ni bimetallic particles. The enhancement is achieved by the upshift of the d-band center of Co-Ni-Fe relative to those of Co-Ni and Ni, meaning easier charge donation to the adsorbate. Furthermore, the exsolved catalyst shows exceptional stability, with continuous DRM operation for about 350 hours.

Versatile Strategy for Tuning ORR Activity of a Single Fe-N4 Site by Controlling Electron-Withdrawing/Donating Properties of a Carbon Plane.

Replacement of Pt-based oxygen reduction reaction (ORR) catalysts with non-precious metal catalysts (NPMCs) such as Fe/N/C is one of the most important issues in the commercialization of proton exchange membrane fuel cells (PEMFCs). Despite numerous studies on Fe/N/C catalysts, a fundamental study on the development of a versatile strategy is still required for tuning the kinetic activity of a single Fe-N4 site. Herein, we report a new and intuitive design strategy for tuning and enhancing the kinetic activity of a single Fe-N4 site by controlling electron-withdrawing/donating properties of a carbon plane with the incorporation of sulfur functionalities. The effect of electron-withdrawing/donating functionalities was elucidated by experimentation and theoretical calculations. Finally, the introduction of an oxidized sulfur functionality decreases the d-band center of iron by withdrawing electrons, thereby facilitating ORR at the Fe-N4 site by lowering the intermediate adsorption energy. Furthermore, this strategy can enhance ORR activity without a decrease in the stability of the catalyst. This simple and straightforward approach can be a cornerstone to develop optimum NPMCs for application in the cathodes of PEMFCs.

Growth Kinetics of Individual Co Particles Ex-solved on SrTi0.75Co0.25O3-δ Polycrystalline Perovskite Thin Films.

A precise control of the size, density, and distribution of metal nanoparticles dispersed on functional oxide supports is critical for promoting catalytic activity and stability in renewable energy and catalysis devices. Here, we measure the growth kinetics of individual Co particles ex-solved on SrTi0.75Co0.25O3-δ polycrystalline thin films under a high vacuum, and at various temperatures and grain sizes using in situ transmission electron microscopy. The ex-solution preferentially occurs at grain boundaries and corners which appear essential for controlling particle density and distribution, and enabling low temperature ex-solution. The particle reaches a saturated size after a few minutes, and the size depends on temperature. Quantitative measurements with a kinetic model determine the rate limiting step, vacancy formation enthalpy, ex-solution enthalpy, and activation energy for particle growth. The ex-solved particles are tightly socketed, preventing interactions among them over 800 °C. Furthermore, we obtain the first direct clarification of the active reaction site for CO oxidation-the Co-oxide interface, agreeing well with density functional theory calculations.

Effect of caffeic acid adsorption in controlling the morphology of gold nanoparticles: role of surface coverage and functional groups.

Caffeic acid (CA) is well known for its strong adsorption on metal or metal oxide surfaces mostly due to the catecholic functional group. On the other hand, the detailed adsorption configurations and the effects of functional groups on molecular adsorption have not been clarified yet. In this study, first-principles calculations were implemented to elucidate the adsorption phenomena of CA and its deprotonated forms on Au(100), (110) and (111), and then predict the morphology of Au nanoparticles (AuNPs). The adsorption energetics and configurations were carefully examined by employing van der Waals interactions to take dispersion forces into consideration. It was found that the adsorption strengths and geometries of the adsorbates are significantly changed by the surface coverages, deprotonated forms, and bound functional groups. These changes in adsorption features induce changes in surface energies, thereby resulting in different morphologies of AuNPs. To accelerate the morphology prediction of AuNPs, we demonstrated that the adsorption energy of CA can be rapidly estimated by the sum of the adsorption energies of the effective functional groups. Our results provide not only fundamental information about the adsorption behaviors of organic molecules on metal surfaces, but also insights for application in the customized synthesis of nanoparticles.

Dynamic Surface Evolution of Metal Oxides for Autonomous Adaptation to Catalytic Reaction Environments.

Metal oxides possessing distinctive physical/chemical properties due to different crystal structures and stoichiometries play a pivotal role in numerous current technologies, especially heterogeneous catalysis for production/conversion of high-valued chemicals and energy. To date, many researchers have investigated the effect of the structure and composition of these materials on their reactivity to various chemical and electrochemical reactions. However, metal oxide surfaces evolve from their initial form under dynamic reaction conditions due to the autonomous behaviors of the constituent atoms to adapt to the surrounding environment. Such nanoscale surface phenomena complicate reaction mechanisms and material properties, interrupting the clarification of the origin of functionality variations in reaction environments. In this review, the current findings on the spontaneous surface reorganization of metal oxides during reactions are categorized into three types: 1) the appearance of nano-sized second phase from oxides, 2) the (partial) encapsulation of oxide atoms toward supported metal surfaces, and 3) the oxide surface reconstruction with selective cation leaching in aqueous solution. Then their effects on each reaction are summarized in terms of activity and stability, providing novel insight for those who design metal-oxide-based catalytic materials.

Highly Reliable 3D Channel Memory and Its Application in a Neuromorphic Sensory System for Hand Gesture Recognition.

Brain-inspired neuromorphic computing systems, based on a crossbar array of two-terminal multilevel resistive random-access memory (RRAM), have attracted attention as promising technologies for processing large amounts of unstructured data. However, the low reliability and inferior conductance tunability of RRAM, caused by uncontrollable metal filament formation in the uneven switching medium, result in lower accuracy compared to the software neural network (SW-NN). In this work, we present a highly reliable CoOx-based multilevel RRAM with an optimized crystal size and density in the switching medium, providing a three-dimensional (3D) grain boundary (GB) network. This design enhances the reliability of the RRAM by improving the cycle-to-cycle endurance and device-to-device stability of the I-V characteristics with minimal variation. Furthermore, the designed 3D GB-channel RRAM (3D GB-RRAM) exhibits excellent conductance tunability, demonstrating high symmetricity (624), low nonlinearity (ßLTP/ßLTD ∼ 0.20/0.39), and a large dynamic range (Gmax/Gmin ∼ 31.1). The cyclic stability of long-term potentiation and depression also exceeds 100 cycles (105 voltage pulses), and the relative standard deviation of Gmax/Gmin is only 2.9%. Leveraging these superior reliability and performance attributes, we propose a neuromorphic sensory system for finger motion tracking and hand gesture recognition as a potential elemental technology for the metaverse. This system consists of a stretchable double-layered photoacoustic strain sensor and a crossbar array neural network. We perform training and recognition tasks on ultrasonic patterns associated with finger motion and hand gestures, attaining a recognition accuracy of 97.9% and 97.4%, comparable to that of SW-NN (99.8% and 98.7%).

The position of lysine controls the catechol-mediated surface adhesion and cohesion in underwater mussel adhesion.

Intensive studies have found that 3,4-dihydroxyphenylalanine (Dopa) is one of the key molecules for underwater mussel adhesion. Although basic mechanisms of mussel adhesion have been elucidated, little is known about how mussels control the balance between surface adhesion and cohesion, which is critical for successful adhesion without peeling and/or tearing. In this work, we focused on lysine (Lys) molecules which are frequently flanked to Dopa residues in interfacial adhesive proteins, specifically their synergy and anti-synergy on surface adhesion and cohesion. Three model peptides were designed to characterize flanking Lys effects. Through nano-mechanistic analyses, we found that flanking Lys enhanced surface adhesion but disrupted Fe3+-mediated cohesion. Through nuclear magnetic resonance analyses and density functional theory calculations, we corroborated the synergetic effect on surface adhesion and anti-synergetic effect on cohesion. We also confirmed the consistency of flanking Lys effects in the actual protein system. Thus, we, for the first time, discovered that each Dopa molecule in interfacial adhesive proteins is participated in surface adhesion and cohesion differently through controlling the existence of flanking Lys. Our discovery enlightens how nature designs adhesive proteins through according roles of Dopa.

Dopant-Driven Positive Reinforcement in Ex-Solution Process: New Strategy to Develop Highly Capable and Durable Catalytic Materials.

The ex-solution phenomenon, a central platform for growing metal nanoparticles on the surface of host oxides in real time with high durability and a fine distribution, has recently been applied to various scientific and industrial fields, such as catalysis, sensing, and renewable energy. However, the high-temperature processing required for ex-solutions (>700 °C) limits the applicable material compositions and has hindered advances in this technique. Here, an unprecedented approach is reported for low-temperature particle ex-solution on important nanoscale binary oxides. WO3 with a nanosheet structure is selected as the parent oxide, and Ir serves as the active metal species that produces the ex-solved metallic particles. Importantly, Ir doping facilitates a phase transition in the WO3 bulk lattice, which further promotes Ir ex-solution at the oxide surface and eventually enables the formation of Ir particles (<3 nm) at temperatures as low as 300 °C. Low-temperature ex-solution effectively inhibits the agglomeration of WO3 sheets while maintaining well-dispersed ex-solved particles. Furthermore, the Ir-decorated WO3 sheets show excellent durability and H2 S selectivity when used as sensing materials, suggesting that this is a generalizable synthetic strategy for preparing highly robust heterogeneous catalysts for a variety of applications.

Highly active dry methane reforming catalysts with boosted in situ grown Ni-Fe nanoparticles on perovskite via atomic layer deposition.

With the need for more stable and active metal catalysts for dry reforming of methane, in situ grown nanoparticles using exsolution are a promising approach. However, in conventional exsolution, most nanoparticles remain underneath the surface because of the sluggish diffusion rate of cations. Here, we report the atomic layer deposition (ALD)-combined topotactic exsolution on La0.6Sr0.2Ti0.85Ni0.15O3-δ toward developing active and durable catalysts. The uniform and quantitatively controlled layer of Fe via ALD facilitates the topotactic exsolution, increasing finely dispersed nanoparticles. The introduction of Fe2O3 yields the formation of Ni-Fe alloy owing to the spontaneous alloy formation energy of -0.43 eV, leading to an enhancement of the catalytic activity for dry methane reforming with a prolonged stability of 410 hours. Overall, the abundant alloy nanocatalysts via ALD mark an important step forward in the evolution of exsolution and its application to the field of energy utilization.

Engineering of Charged Defects at Perovskite Oxide Surfaces for Exceptionally Stable Solid Oxide Fuel Cell Electrodes.

Cation segregation, particularly Sr segregation, toward a perovskite surface has a significant effect on the performance degradation of a solid oxide cell (solid oxide electrolysis/fuel cell). Among the number of key reasons generating the instability of perovskite oxide, surface-accumulated positively charged defects (oxygen vacancy, Vo··) have been considered as the most crucial drivers in strongly attracting negatively charged defects (SrA - site') toward the surface. Herein, we demonstrate the effects of a heterointerface on the redistribution of both positively and negatively charged defects for a reduction of Vo·· at a perovskite surface. We took Sm0.5Sr0.5CoO3-δ (SSC) as a model perovskite film and coated Gd0.1Ce0.9O2-δ (GDC) additionally onto the SSC film to create a heterointerface (GDC/SSC), resulting in an ∼11-fold reduction in a degradation rate of ∼8% at 650 °C and ∼10-fold higher surface exchange (kq) than a bare SSC film after 150 h at 650 °C. Using X-ray photoelectron spectroscopy and electron energy loss spectroscopy, we revealed a decrease in positively charged defects of Vo·· and transferred electrons in an SSC film at the GDC/SSC heterointerface, resulting in a suppression of negatively charged Sr (SrSm') segregation. Finally, the energetic behavior, including the charge transfer phenomenon, O p-band center, and oxygen vacancy formation energy calculated using the density functional theory, verified the effects of the heterointerface on the redistribution of the charged defects, resulting in a remarkable impact on the stability of perovskite oxide at elevated temperatures.

A new etching process for zinc oxide with etching rate and crystal plane control: experiment, calculation, and membrane application.

The etching process can be a useful method for the morphology control of nanostructures. Using precise experiments and theoretical calculations, we report a new ZnO etching process triggered by the reaction of ZnO with transition metal cations and demonstrate that the etching rate and direction could be controlled by varying the kind of transition metal cation. In addition, the developed etching process was introduced to form a thin and uniform ZnO layer, which was utilized for the fabrication of an improved propylene-selective ZIF-8 membrane via conversion seeding and secondary growth.

Cation-swapped homogeneous nanoparticles in perovskite oxides for high power density.

Exsolution has been intensively studied in the fields of energy conversion and storage as a method for the preparation of catalytically active and durable metal nanoparticles. Under typical conditions, however, only a limited number of nanoparticles can be exsolved from the host oxides. Herein, we report the preparation of catalytic nanoparticles by selective exsolution through topotactic ion exchange, where deposited Fe guest cations can be exchanged with Co host cations in PrBaMn1.7Co0.3O5+δ. Interestingly, this phenomenon spontaneously yields the host PrBaMn1.7Fe0.3O5+δ, liberating all the Co cations from the host owing to the favorable incorporation energy of Fe into the lattice of the parent host (ΔEincorporation = -0.41 eV) and the cation exchange energy (ΔEexchange = -0.34 eV). Remarkably, the increase in the number of exsolved nanoparticles leads to their improved catalytic activity as a solid oxide fuel cell electrode and in the dry reforming of methane.

A Simple Descriptor to Rapidly Screen CO Oxidation Activity on Rare-Earth Metal-Doped CeO2: From Experiment to First-Principles.

Ceria (CeO2) is an attractive catalyst because of its unique properties, such as facile redoxability and high stability. Thus, many researchers have examined a wide range of catalytic reactions on ceria nanoparticles (NPs). Among those contributions are the reports of the dopant-dependent catalytic activity of ceria. On the other hand, there have been few mechanistic studies of the effects of a range of dopants on the chemical reactivity of ceria NPs. In this study, we examined the catalytic activities of pure and Pr, Nd, and Sm-doped CeO2 (PDC, NDC, and SDC, respectively) NPs on carbon monoxide (CO) oxidation. Density functional theory (DFT) calculations were also performed to elucidate the reaction mechanism on rare-earth (RE)-doped CeO2(111). The experimental results showed that the catalytic activities of CO oxidation were in the order of CeO2 > PDC > NDC > SDC. This is consistent with the DFT results, where the reaction is explained by the Mars-van Krevelen mechanism. On the basis of the theoretical interpretation of the experimental results, the ionic radius of the RE dopant can be used as a simple descriptor to predict the energy barrier at the rate-determining step, thereby predicting the entire reaction activity. Using the descriptor, a wide range of RE dopants on CeO2(111) were screened for CO oxidation. These results provide useful insights to unravel the CO oxidation activity on various oxide catalysts.

Exsolution trends and co-segregation aspects of self-grown catalyst nanoparticles in perovskites.

In perovskites, exsolution of transition metals has been proposed as a smart catalyst design for energy applications. Although there exist transition metals with superior catalytic activity, they are limited by their ability to exsolve under a reducing environment. When a doping element is present in the perovskite, it is often observed that the surface segregation of the doping element is changed by oxygen vacancies. However, the mechanism of co-segregation of doping element with oxygen vacancies is still an open question. Here we report trends in the exsolution of transition metal (Mn, Co, Ni and Fe) on the PrBaMn2O5+δ layered perovskite oxide related to the co-segregation energy. Transmission electron microscopic observations show that easily reducible cations (Mn, Co and Ni) are exsolved from the perovskite depending on the transition metal-perovskite reducibility. In addition, using density functional calculations we reveal that co-segregation of B-site dopant and oxygen vacancies plays a central role in the exsolution.

Concentration Effect of Reducing Agents on Green Synthesis of Gold Nanoparticles: Size, Morphology, and Growth Mechanism.

Under various concentration conditions of reducing agents during the green synthesis of gold nanoparticles (AuNPs), we obtain the various geometry (morphology and size) of AuNPs that play a crucial role in their catalytic properties. Through both theoretical and experimental approaches, we studied the relationship between the concentration of reducing agent (caffeic acid) and the geometry of AuNPs. As the concentration of caffeic acid increases, the sizes of AuNPs were decreased due to the adsorption and stabilizing effect of oxidized caffeic acids (OXCAs). Thus, it turns out that optimal concentration exists for the desired geometry of AuNPs. Furthermore, we investigated the growth mechanism for the green synthesis of AuNPs. As the caffeic acid is added and adsorbed on the surface of AuNPs, the aggregation mechanism and surface free energy are changed and consequently resulted in the AuNPs of various geometry.

Cold welding of gold nanoparticles on mica substrate: Self-adjustment and enhanced diffusion.

From the images of HR-TEM, FE-SEM, and AFM, the cold welding of gold nanoparticles (AuNPs) on a mica substrate is observed. The cold-welded gold nanoparticles of 25 nm diameters are found on the mica substrate in AFM measurement whereas the size of cold welding is limited to 10 nm for nanowires and 2~3 nm for nanofilms. Contrary to the nanowires requiring pressure, the AuNPs are able to rotate freely due to the attractive forces from the mica substrate and thus the cold welding goes along by adjusting lattice structures. The gold nanoparticles on the mica substrate are numerically modeled and whose physical characteristics are obtained by the molecular dynamic simulations of LAMMPS. The potential and kinetic energies of AuNPs on the mica substrate provide sufficient energy to overcome the diffusion barrier of gold atoms. After the cold welding, the regularity of lattice structure is maintained since the rotation of AuNPs is allowed due to the presence of mica substrate. It turns out that the growth of AuNPs can be controlled arbitrarily and the welded region is nearly perfect and provides the same crystal orientation and strength as the rest of the nanostructures.