Molecular dynamics of liquid-electrode interface by integrating Coulomb interaction into universal neural network potential.

Computational understanding of the liquid-electrode interface faces challenges in efficiently incorporating reactive force fields and electrostatic potentials within reasonable computational costs. Although universal neural network potentials (UNNPs), representing pretrained machine learning interatomic potentials, are emerging, current UNNP models lack explicit treatment of Coulomb potentials, and methods for integrating additional charges on the electrode remain to be established. We propose a method to analyze liquid-electrode interfaces by integrating a UNNP, known as the preferred potential, with Coulomb potentials using the ONIOM method. This approach extends the applicability of UNNPs to electrode-liquid interface systems. Through molecular dynamics simulations of graphene-water and graphene oxide (GO)-water interfaces, we demonstrate the effectiveness of our method. Our findings emphasize the necessity of incorporating long-range Coulomb potentials into the water potential to accurately describe water polarization at the interface. Furthermore, we observe that functional groups on the GO electrode influence both polarization and capacitance.

Molybdenum-Ruthenium-Carbon Solid-Solution Alloy Nanoparticles: Can They Be Pseudo-Technetium Carbide?

Technetium (Tc), atomic number 43, is an element that humans cannot freely use even in the 21st century because Tc is radioactive and has no stable isotope. In this report, we present molybdenum-ruthenium-carbon solid-solution alloy (MoxRu1-xCy) nanoparticles (NPs) that are expected to have an electronic structure similar to that of technetium carbide (TcCy). MoxRu1-xCy NPs were synthesized by annealing under a helium/hydrogen atmosphere following thermal decomposition of metal precursors. The obtained NPs had a solid-solution structure in the whole composition range. MoxRu1-xCy with a cubic structure (down to 30 atom % Mo in the metal ratio) showed a superconducting state, and the transition temperature (Tc) increased with increasing Mo composition. The continuous change in Tc across that of TcCy indicates the continuous control of the electronic structure by solid-solution alloying, leading to pseudo-TcCy. Density functional theory calculations indicated that the synthesized Mo0.53Ru0.47C0.41 has a similar electronic structure to TcC0.41.

Noble-Metal High-Entropy-Alloy Nanoparticles: Atomic-Level Insight into the Electronic Structure.

The compositional space of high-entropy-alloy nanoparticles (HEA NPs) significantly expands the diversity of the materials library. Every atom in HEA NPs has a different elemental coordination environment, which requires knowledge of the local electronic structure at an atomic level. However, such structure has not been disclosed experimentally or theoretically. We synthesized HEA NPs composed of all eight noble-metal-group elements (NM-HEA) for the first time. Their electronic structure was revealed by hard X-ray photoelectron spectroscopy and density function theory calculations with NP models. The NM-HEA NPs have a lower degeneracy in energy level compared with the monometallic NPs, which is a common feature of HEA NPs. The local density of states (LDOS) of every surface atom was first revealed. Some atoms of the same constituent element in HEA NPs have different LDOS profiles, whereas atoms of other elements have similar LDOS profiles. In other words, one atom in HEA loses its elemental identity and it may be possible to create an ideal LDOS by adjusting the neighboring atoms. The tendency of the electronic structure change was shown by supervised learning. The NM-HEA NPs showed 10.8-times higher intrinsic activity for hydrogen evolution reaction than commercial Pt/C, which is one of the best catalysts.

Thermodynamic stability of Pd-Ru alloy nanoparticles: combination of density functional theory calculations, supervised learning, and Wang-Landau sampling.

Solid-solution alloy nanoparticles (NPs) comprising Pd and Ru, which are immiscible in the bulk state, have been synthesised and show excellent catalytic performance. To date, most studies have evaluated the stability of alloy NPs at 0 K only. Because the thermodynamic stability of Pd-Ru alloy NPs may differ from that of the alloy in the bulk state, the stable configuration of the NPs must be evaluated under a finite temperature. Such stability evaluations are critical for developing the durable NPs as catalysts. Therefore, the thermodynamic stability of Pd-Ru alloy NPs was analysed using density functional theory (DFT), supervised learning (SL), and Wang-Landau sampling. We calculated the excess energy of Pd-Ru alloy NPs, which depends on their composition, structure, NP size, adatom type, and defects, and applied SL to all models. The excess energies of the Pd-Ru alloy NPs expressed by structural information, such as the surface-to-volume ratio, correlated with those calculated using DFT. Wang-Landau sampling based on the energy estimated by SL gave the thermodynamic stability of Pd-Ru alloy NPs with a stable configuration under a finite temperature. The solid-solution atomic configuration was subdivided into partially mixed configurations in the surface layer or in the core of the NPs, which is different from the bulk state. The partially mixed configuration was determined by the overall composition and surface properties. The findings from the combined method could contribute to a better understanding of the alloy-NP stability and their application in catalysis.

Improving the performance of silicon monoxide anodes via tuning a multiple pre-doping system: a first-principles study.

Silicon monoxide is a potentially viable anode material for high-performance lithium-ion batteries (LIBs). However, a low initial coulombic efficiency and large volume expansion limit its commercial application. Pre-lithiation is an efficient solution, but is expensive because of limited "pre-lithiation" sources. In this work, we theoretically investigated a novel multiple pre-doping SiO system (Li-NaMg-SiO). By comparing its lithiation behavior to that of the traditional Li-doping system (Li-SiO), we revealed the different doping effects during lithiation. Similar to the traditional Li-doping system, the insertion of Na and Mg disintegrates the Si-O host matrix to form Na-O and Mg-O bonds and active Si clusters. At the end of lithiation, the O-Li coordination number (CN) tends to saturate at CNO-Li ≈ 5 in Li-Na-SiO, Li-Mg-SiO, and Li-NaMg-SiO systems, while the value of CNO-Li in the Li-SiO system is more than 6, which suggests that there are reorganizations between Li, Na, and Mg in the silicate matrix. Doping sources of both Na and Mg can prevent the active Li ions from being trapped by O-Li bonds and increase the initial coulombic efficiency. From the density of states (DOS), we notice that all the different pre-doping systems have similar electronic structures, and they can be expected to undergo the same lithiation process. Furthermore, the higher ion-conductivity and smaller volume expansion during the lithiation process characterized by root mean square deviation (RMSD) and volume analysis prove the advantages of the binary doping system (Li-NaMg-SiO) for the improvement of cycle stability for Si-based materials. These advantages benefit from the loose and amorphous structures of doping systems during lithiation. Our work highlights the doping effects of multiple sources and the promotion of "inert compounds" on the entire lithiation process, which provide valuable insight for high-performance anode design.

Rational Synthesis for a Noble Metal Carbide.

Transition metal carbides have attractive physical and chemical properties that are much different from their parent metals. Particularly, noble metal carbides are expected to be promising materials for a variety of applications, particularly as efficient catalysts. However, noble metal carbides have rarely been obtained because carbide phases do not appear in noble metal-carbon phase diagrams and a reasonable synthesis method to make noble metal carbides has not yet been established. Here, we propose a new synthesis method for noble metal carbides and describe the first synthesis of rhodium carbide using tetracyanoethylene (TCNE). The rhodium carbide was synthesized without extreme conditions, such as the very high temperature and/or pressure typically required in conventional carbide syntheses. Moreover, we investigated the electronic structure and catalytic activity for the hydrogen evolution reaction (HER). We found that rhodium carbide has much higher catalytic activity for HER than pure Rh. Our study provides a feasible strategy to create new metal carbides to help advance the field of materials science.

A CO Adsorption Site Change Induced by Copper Substitution in a Ruthenium Catalyst for Enhanced CO Oxidation Activity.

Ru is an important catalyst in many types of reactions. Specifically, Ru is well known as the best monometallic catalyst for oxidation of carbon monoxide (CO) and has been practically used in residential fuel cell systems. However, Ru is a minor metal, and the supply risk often causes violent fluctuations in the price of Ru. Performance-improved and cost-reduced solid-solution alloy nanoparticles of the Cu-Ru system for CO oxidation are now presented. Over the whole composition range, all of the Cux Ru1-x nanoparticles exhibit significantly enhanced CO oxidation activities, even at 70 at % of inexpensive Cu, compared to Ru nanoparticles. Only 5 at % replacement of Ru with Cu provided much better CO oxidation activity, and the maximum activity was achieved by 20 at % replacement of Ru by Cu. The origin of the high catalytic performance was found as CO site change by Cu substitution, which was investigated using in situ Fourier transform infrared spectra and theoretical calculations.

Theoretical study of tetrahedral site occupation by hydrogen in Pd nanoparticles.

To understand the enhanced effects and new hydrogen absorption properties of metal nanoparticles, we theoretically investigated the hydrogen absorption in Pd nanoparticles, adopting the Pd405 model of ca. 2.5 nm by using density functional theory. Pd405 showed inhomogeneous geometric features, especially near the surface region. The hydrogen absorptions in octahedral (O) and tetrahedral (T) sites near the core region were stable and unstable, respectively, similar to the Pd bulk. We clearly demonstrated the possibility of hydrogen absorption in T sites near the surface of Pd405. The flexible volume change and the difference in hydrogen position relative to the center of mass of the T site that we observed are important factors for stable hydrogen absorption in T sites of Pd nanoparticles. In addition, we discuss the differences in hydrogen diffusion mechanisms in the core and near surface regions, based on the stability of hydrogen absorption in O and T sites.

Solid-Solution Alloy Nanoparticles of the Immiscible Iridium-Copper System with a Wide Composition Range for Enhanced Electrocatalytic Applications.

For the first time, we synthesize solid-solution alloy nanoparticles of Ir and Cu with a size of ca. 2 nm, despite Ir and Cu being immiscible in the bulk up to their melting over the whole composition range. We performed a systematic characterization on the nature of the Irx Cu1-x solid-solution alloys using powder X-ray diffraction, scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. The results showed that the Irx Cu1-x alloys had a face-centered-cubic structure; charge transfer from Cu to Ir occurred in the alloy nanoparticles, as the core-level Ir 4f peaks shifted to lower energy region with the increase in Cu content. Furthermore, we observed that the alloying of Ir with Cu enhanced both the electrocatalytic oxygen evolution and oxygen reduction reactions. The enhanced activities could be attributed to the electronic interaction between Ir and Cu arising from the alloying effect at atomic-level.

Image contrast enhancement of Ni/YSZ anode during the slice-and-view process in FIB-SEM.

Focused ion beam-scanning electron microscopy (FIB-SEM) is a widely used and easily operational equipment for three-dimensional reconstruction with flexible analysis volume. It has been using successfully and increasingly in the field of solid oxide fuel cell. However, the phase contrast of the SEM images is indistinct in many cases, which will bring difficulties to the image processing. Herein, the phase contrast of a conventional Ni/yttria stabilized zirconia anode is tuned in an FIB-SEM with In-Lens secondary electron (SE) and backscattered electron detectors. Two accessories, tungsten probe and carbon nozzle, are inserted during the observation. The former has no influence on the contrast. When the carbon nozzle is inserted, best and distinct contrast can be obtained by In-Lens SE detector. This method is novel for contrast enhancement. Phase segmentation of the image can be automatically performed. The related mechanism for different images is discussed.

Why solid oxide cells can be reversibly operated in solid oxide electrolysis cell and fuel cell modes?

High temperature solid oxide cells (SOCs) are attractive for storage and regeneration of renewable energy by operating reversibly in solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes. However, the stability of SOCs, particularly the deterioration of the performance of oxygen electrodes in the SOEC operation mode, is the most critical issue in the development of high performance and durable SOCs. In this study, we investigate in detail the electrochemical activity and stability of La0.8Sr0.2MnO3 (LSM) oxygen electrodes in cyclic SOEC and SOFC modes. The results show that the deterioration of LSM oxygen electrodes caused by anodic polarization can be partially or completely recovered by subsequent cathodic polarization. Using in situ assembled LSM electrodes without pre-sintering, we demonstrate that the deteriorated LSM/YSZ interface can be repaired and regenerated by operating the cells under cathodic polarization conditions. This study for the first time establishes the foundation for the development of truly reversible and stable SOCs for hydrogen fuel production and electricity generation in cyclic SOEC and SOFC operation modes.

Phase Control of Solid-Solution Nanoparticles beyond the Phase Diagram for Enhanced Catalytic Properties.

The crystal structure, which intrinsically affects the properties of solids, is determined by the constituent elements and composition of solids. Therefore, it cannot be easily controlled beyond the phase diagram because of thermodynamic limitations. Here, we demonstrate the first example of controlling the crystal structures of a solid-solution nanoparticle (NP) entirely without changing its composition and size. We synthesized face-centered cubic (fcc) or hexagonal close-packed (hcp) structured Pd x Ru1-x NPs (x = 0.4, 0.5, and 0.6), although they cannot be synthesized as bulk materials. Crystal-structure control greatly improves the catalytic properties; that is, the hcp-Pd x Ru1-x NPs exceed their fcc counterparts toward the oxygen evolution reaction (OER) in corrosive acid. These NPs only require an overpotential (η) of 200 mV at 10 mA cm-2, can maintain the activity for more than 20 h, greatly outperforming the fcc-Pd0.4Ru0.6 NPs (η = 280 mV, 9 min), and are among the most efficient OER catalysts reported. Synchrotron X-ray-based spectroscopy, atomic-resolution electron microscopy, and density functional theory (DFT) calculations suggest that the enhanced OER performance of hcp-PdRu originates from the high stability against oxidative dissolution.

An Element-Based Generalized Coordination Number for Predicting the Oxygen Binding Energy on Pt3M (M = Co, Ni, or Cu) Alloy Nanoparticles.

We studied the binding energies of O species on face-centered-cubic Pt3M nanoparticles (NPs) with a Pt-skin layer using density functional theory calculations, where M is Co, Ni, or Cu. It is desirable to express the property by structural parameters rather than by calculated electronic structures such as the d-band center. A generalized coordination number (GCN) is an effective descriptor to predict atomic or molecular adsorption energy on Pt-NPs. The GCN was extended to the prediction of highly active sites for oxygen reduction reaction. However, it failed to explain the O binding energies on Pt-skin Pt150M51-NPs. In this study, we introduced an element-based GCN, denoted as GCNA-B, and considered it as a descriptor for supervised learning. The obtained regression coefficients of GCNPt-Pt were smaller than those of the other GCNA-B. With increasing M atoms in the subsurface layer, GCNPt-M, GCNM-Pt, and GCNM-M increased. These factors could reproduce the calculated result that the O binding energies of the Pt-skin Pt150M51-NPs were less negative than those of the Pt201-NPs. Thus, GCNA-B explains the ligand effect of the O binding energy on the Pt-skin Pt150M51-NPs.

Density Functional Theory and Machine Learning Description and Prediction of Oxygen Atom Chemisorption on Platinum Surfaces and Nanoparticles.

Elucidating chemical interactions between catalyst surfaces and adsorbates is crucial for understanding surface chemical reactivity. Herein, interactions between O atoms and Pt surfaces and nanoparticles are described as a linear combination of the properties of pristine surfaces and isolated nanoparticles. The energetics of O chemisorption onto Pt surfaces were described using only two descriptors related to surface geometrical features. The relatively high coefficient of determination and low mean absolute error between the density functional theory-calculated and predicted O binding energies indicate good accuracy of the model. For Pt nanoparticles, O binding is described by the geometrical features and electronic properties of isolated nanoparticles. Using a linear combination of five descriptors and accounting for nanoparticle size effects and adsorption site types, the O binding energy was estimated with a higher accuracy than with conventional single-descriptor models. Finally, these five descriptors were used in a general model that decomposes O binding energetics on Pt surfaces and nanoparticles. Good correlation was achieved between the calculated and predicted O binding energies, and model validation confirmed its accuracy. This is the first model that considers the nanoparticle size effect and all possible adsorption sites on Pt nanoparticles and surfaces.

Highly Stable and Active Solid-Solution-Alloy Three-Way Catalyst by Utilizing Configurational-Entropy Effect.

Since 1970, people have been making every endeavor to reduce toxic emissions from automobiles. After the development of a three-way catalyst (TWC) that concurrently converts three harmful gases, carbon monoxide (CO), hydrocarbons (HCs), and nitrogen oxides (NOx ), Rh became an essential element in automobile technology because only Rh works efficiently for catalytic NOx reduction. However, due to the sharp price spike in 2007, numerous efforts have been made to replace Rh in TWCs. Nevertheless, Rh remains irreplaceable, and now, the price of Rh is increasing significantly again. Here, it is demonstrated that PdRuM ternary solid-solution alloy nanoparticles (NPs) exhibit highly durable and active TWC performance, which will result in a significant reduction in catalyst cost compared to Rh. This work provides insights into the design of highly durable and efficient functional alloy NPs, guiding how to best take advantage of the configurational entropy in addition to the mixing enthalpy.

Quantum chemistry study on absorption spectra, electronic and electrical properties of organic dye on anatase(001).

As the most reactive surface, the stoichiometric O-bridge terminated anatase(001) surface attracted considerable attentions in many application fields. The interfacial electron transfer in dye-sensitized anatase(001) plays a principal role in a variety of photoinduced reactions. In the present work, the UV-vis absorption spectrum of TiO2 bulk and different surface models were calculated by means of tight-binding quantum chemical molecular dynamics program "Colors-excite" for the first time. The thickness dependence on electronic and electrical properties of anatase(001) surface was achieved. The anatase(001) surface with a thickness of 1.0 nm shows excellent electronic and electrical properties. Moreover, the most suitable binding mode (dissociative adsorption) and absorption spectra of perylene with acrylic acid (PAA) on the optimum anatase(001) were investigated. A significant red-shift was observed from the UV-vis absorption spectrum of PAA/anatase(001) system. The red-shift occurring when PAA adsorbed on anatase(001) surface suggests that PAA/anatase(001) may be potential candidate for dye-sensitized solar cell. This study also proposed an effective computational tool "Colors-excite" to study of the electronic excitation properties for both molecular and periodic systems.

Tribochemical reaction dynamics of molybdenum dithiocarbamate on nascent iron surface: a hybrid quantum chemical/classical molecular dynamics study.

Using a hybrid quantum chemical/classical molecular dynamics method, we have studied the tribochemical reaction dynamics of molybdenum dithiocarbamate (MoDTC), a commonly used friction modifier in automobile engine oils. MoDTC molecule adsorbed on rubbing nascent iron surface was situated. We firstly investigated the dynamic behavior of MoDTC molecule on the rubbing Fe(001) surface. During the friction simulation, the elongation of Mo-O bonds was observed, forming the Mo2S4 and thiocarbamic acid molecules. To unveil the detailed mechanism of this bond elongation, the electronic states of the MoDTC molecule and Fe(001) surface were computed, and the catalytic effects of Fe(001) surface to the molecule was found. We also found that extreme friction would influence the complete Mo-O bond dissociation. By using the hybrid quantum chemical/classical molecular dynamics method, we successfully simulated the tribochemical reaction dynamics of MoDTC as a friction modifier and obtained the influences of nascent iron surface and friction on its chemical reaction.

Theoretical design of a technetium-like alloy and its catalytic properties.

Based on the concept of density of states (DOS) engineering, we theoretically designed a pseudo-Tc material (Mo-Ru alloy) and investigated its electronic structure, phase stability and catalytic activity by using density functional theory. Through comparing the DOS shape, peak distribution, and DOS area differences between Tc and the Mo-Ru alloy, we noticed that bcc-Mo8Ru8 and hcp-Mo8Ru8 had the most similar electronic structures to Tc. The excess energies after entropy correction of hcp-Mo8Ru8 and bcc-Mo8Ru8 are stable when the temperature is up to 765 and 745 K, respectively. These results provided the possibility of pseudo-Tc alloy (hcp-Mo8Ru8 and bcc-Mo8Ru8) synthesis. Finally, according to reaction coordinate analysis, the similar catalytic activity between hcp-Mo8Ru8 and Tc have been demonstrated in CO oxidation and N2 dissociation. In N2 dissociation, Tc has a suitable ratio of transition state (TS) barrier to reaction energy which make Tc an efficient catalyst for NH3 synthesis, in addition to our designed pseudo-Tc (hcp-MoRu) because of the similar electronic structures. Our finding provides valuable insight into materials and catalyst design.

Multiyear microgrid data from a research building in Tsukuba, Japan.

Microgrids comprising renewable energy technologies are often modelled and optimised from a theoretical point of view. Verification of theoretical systems with data of actually implemented systems in the field rarely occurs in an open manner, especially on the intermediate scale of research buildings. To enable modelling of the actual microgrid performance of a research environment, we present a multiyear dataset of a microgrid with solar arrays and a battery. The main energy datasets comprise data per second supplemented by hourly solar irradiation data. These may be combined with data concerning the hourly electricity prices from the main grid and the low-electricity-price periods of national holidays. The level of detail of the data per second in combination with the hourly data in these datasets allows for a comparison to the efficiency and weather-parameter correlation of other renewable energy technologies, as well as forecasting future energy generation and consumption.

Emergence of high ORR activity through controlling local density-of-states by alloying immiscible Au and Ir.

The electronic structure of surface atoms has a great effect on catalytic activity because the binding energy of reactants is closely related to the electronic structure. Therefore, designing and controlling the local density of states (LDOS) of the catalyst surface would be a rational way to develop innovative catalysts. Herein, we first demonstrate a highly active AuIr solid-solution alloy electrocatalyst for the oxygen reduction reaction (ORR) by emulating the Pt LDOS profile. The calculated LDOS of Ir atoms on the Au0.5Ir0.5(111) surface closely resembled that of Pt(111), resulting in suitable oxygen adsorption energy on the alloy surface for the ORR. We successfully synthesized AuIr solid-solution alloys, while Ir and Au are immiscible even above their melting points in the bulk state. Although monometallic Ir or Au is not active for the ORR, the synthesized Au0.5Ir0.5 alloy demonstrated comparable activity to Pt at 0.9 V versus a reversible hydrogen electrode.