Partial oxidation of Step-Bound Water Leads to Anomalous pH Effects on Metal Electrode Step-Edges

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. Here, we analyze the change in charge and free energies upon adsorption using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (Hupd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.Comment: 9 pages, 8 figures and 3 table

Insights into the Nature of Synergistic Effects in Proton-Conducting 4,4−1H,1H-Bitriazole-Poly(ethylene oxide) Composites

A nitrogen-containing heterocycle (NCH), 4,4-1H-1H-bi-1,2,3-triazole (bitriazole), capable of mimicking the hydrogen bonding of water in the solid state is synthesized and its ability to conduct protons in the presence of poly(ethylene oxides) under anhydrous conditions is investigated. Bitriazole is shown to have sufficient thermal and electrochemical stability for fuel cell applications. The composites formed between bitriazole and poly(ethylene oxides) give proton conductivities that can be described by the Vogel−Tamman−Fulcher (VTF) equation. These characteristics suggest coupling between polymer segmental motion and ion transport. The bitriazole N-H proton is shown to be the source of conductivity, and bitriazole and poly(ethylene oxides) function synergistically through specific intermolecular interactions and polymer-induced segmental motion to create a pathway for proton transport via structural diffusion

C-E Translation of Buzzwords From the Perspective of Eco-Translatology

Buzzwords, the popular words and expressions, spread widely among the public, as the comprehensive product of society, culture and language, and it has become a new research subject in recent years. This paper analyzes the C-E translation of buzzwords from the perspective of Eco-translatology. Three-dimensional transformations of Eco-translatology provide a new aspect for us to improve the translation of buzzwords. Targeted readers will understand the translated version of buzzwords as much as possible if transformations were made from linguistic, cultural and communicative dimensions

R&D modes and firm performance in high-tech companies: A research based on cross-boundary ambidexterity and network structures

This paper draws on the cross-boundary ambidexterity theory to propose that four different R&D modes impact firm performance differently and that cooperative network structure moderates the above relationships. The theoretical model is tested by using financial and patent data of 587 high-tech firms for 10 consecutive years in China. We find that different R&D modes have different impacts on a firm’s financial and innovative performance, and network structure plays different moderating roles. Practically, this work guides high-tech enterprises to optimize their resource allocation, select the most appropriate R&D mode, and establish efficient cooperative networks

Sodium Diffusion through Aluminum-Doped Zeolite BEA System: Effect of Water Solvation

To investigate the effect of hydration on the diffusion of sodium ions through the aluminum-doped zeolite BEA system (Si/Al = 30), we used the grand canonical Monte Carlo (GCMC) method to predict the water absorption into aluminosilicate zeolite structure under various conditions of vapor pressure and temperature, followed by molecular dynamics (MD) simulations to investigate how the sodium diffusion depends on the concentration of water molecules. The predicted absorption isotherm shows first-order-like transition, which is commonly observed in hydrophobic porous systems. The MD trajectories indicate that the sodium ions diffuse through zeolite porous structures via hopping mechanism, as previously discussed for similar solid electrolyte systems. These results show that above 15 wt % hydration (good solvation regime) the formation of the solvation cage dramatically increases sodium diffusion by reducing the hopping energy barrier by 25% from the value of 3.8 kcal/mol observed in the poor solvation regime

UWB-INS Fusion Positioning Based on a Two-Stage Optimization Algorithm

Ultra-wideband (UWB) is a carrier-less communication technology that transmits data using narrow pulses of non-sine waves on the nanosecond scale. The UWB positioning system uses the multi-lateral positioning algorithm to accurately locate the target, and the positioning accuracy is seriously affected by the non-line-of-sight (NLOS) error. The existing non-line-of-sight error compensation methods lack multidimensional consideration. To combine the advantages of various methods, a two-stage UWB-INS fusion localization algorithm is proposed. In the first stage, an NLOS signal filter is designed based on support vector machines (SVM). In the second stage, the results of UWB and Inertial Navigation System (INS) are fused based on Kalman filter algorithm. The two-stage fusion localization algorithm achieves a great improvement on positioning system, it can improve the localization accuracy by 79.8% in the NLOS environment and by 36% in the (line-of-sight) LOS environment

Proton conductivity of acid-functionalized zeolite beta, MCM-41, and MCM-48 : effect of acid strength

Direct methanol fuel cells (DMFCs) and hydrogen proton exchange membrane fuel cells (PEMFCs) are two types of fuel cells where commercial products have been developed, but have yet to find widespread deployment. Although these devices are compact, easily refuelable, and operate at comparatively low temperatures, problems such as catalyst poisoning, methanol crossover, and water management exist and are current topics of research. One important component of both the DMFC and PEMFC is a protonically conducting but electronically insulating membrane placed between the anode and cathode. To minimize internal ohmic losses, the membrane must possess a high proton conductivity, and is commonly formed from Nafion or other perfluorosulfonic acid polymers. When fully hydrated, these polymers exhibit proton conductivites on the order of 1 × 10^(-1) to 1 × 10^(−2) S/cm. For hydrogen PEMFC without active humidification, proton conductivity decreases rapidly with increasing temperaure. For DMFC, membrane swelling allows methanol diffusion directly from anode to cathode decreasing cell efficiency

Thermal Conductivity of Pure Silica MEL and MFI Zeolite Thin Films

This paper reports the room temperature cross-plane thermal conductivity of pure silica zeolite (PSZ) MEL and MFI thin films. PSZ MEL thin films were prepared by spin coating a suspension of MEL nanoparticles in 1-butanol solution onto silicon substrates followed by calcination and vapor-phase silylation with trimethylchlorosilane. The mass fraction of nanoparticles within the suspension varied from 16% to 55%. This was achieved by varying the crystallization time of the suspension. The thin films consisted of crystalline MEL nanoparticles embedded in a nonuniform and highly porous silica matrix. They featured porosity, relative crystallinity, and MEL nanoparticles size ranging from 40% to 59%, 23% to 47% and 55 nm to 80 nm, respectively. PSZ MFI thin films were made by in situ crystallization, were b-oriented, fully crystalline, and had a 33% porosity. Thermal conductivity of these PSZ thin films was measured at room temperature using the 3ω method. The cross-plane thermal conductivity of the MEL thin films remained nearly unchanged around 1.02±0.10 W m−1 K−1 despite increases in (i) relative crystallinity, (ii) MEL nanoparticle size, and (iii) yield caused by longer nanoparticle crystallization time. Indeed, the effects of these parameters on the thermal conductivity were compensated by the simultaneous increase in porosity. PSZ MFI thin films were found to have similar thermal conductivity as MEL thin films even though they had smaller porosity. Finally, the average thermal conductivity of the PSZ films was three to five times larger than that reported for amorphous sol-gel mesoporous silica thin films with similar porosity and dielectric constant