The structure of the electrical double layer has been debated for well over a century, since it mediates colloidal interactions, regulates surface structure, controls reactivity, sets capacitance, and represents the central element of electrochemical supercapacitors. The surface potential of such surfaces generally exceeds the electrokinetic potential, often substantially. Traditionally, a Stern layer of nonspecifically adsorbed ions has been invoked to rationalize the difference between these two potentials; however, the inability to directly measure the surface potential of dispersed systems has rendered quantitative measurements of the Stern layer potential, and other quantities associated with the outer Helmholtz plane, impossible. Here, we use x-ray photoelectron spectroscopy from a liquid microjet to measure the absolute surface potentials of silica nanoparticles dispersed in aqueous electrolytes. We quantitatively determine the impact of specific cations (Li þ , Na þ , K þ , and Cs þ ) in chloride electrolytes on the surface potential, the location of the shear plane, and the capacitance of the Stern layer. We find that the magnitude of the surface potential increases linearly with the hydrated-cation radius. Interpreting our data using the simplest assumptions and most straightforward understanding of Gouy-Chapman-Stern theory reveals a Stern layer whose thickness corresponds to a single layer of water molecules hydrating the silica surface, plus the radius of the hydrated cation. These results subject electrical double-layer theories to direct and falsifiable tests to reveal a physically intuitive and quantitatively verified picture of the Stern layer that is consistent across multiple electrolytes and solution conditions.
Nickel oxide yttria‐stabilized zirconia (NiO–YSZ) anode materials were synthesized via hydrolysis of the corresponding chloride solutions with NH3, NH3+NaOH, and NaOH as precipitation agents. Powder properties such as crystallite size, morphology, and sintering behavior of the final NiO–YSZ materials were also studied. The mechanism of the formation of NiO–YSZ was established for the different co‐precipitation techniques by the direct observation of Ni(NH3)n+2 complexes, Ni(OH)2 and NiO at different stages of the synthesis process. A direct relationship between the precipitation agent, the order of calcination from dry sample to final product, the final composition, the crystallite sizes and particle sizes of NiO, and the sinterability of the final products was established. A comparison of the powder and individual component properties indicate that the choice of precipitation agent greatly influences the final characteristics. Ni/YSZ materials prepared by NH3+NaOH precipitation offer higher Ni dispersion and nanocrystallinity of both the Ni and YSZ phases. The conductivity of both prepared materials compares well with mixed‐oxide materials of higher Ni content.
Preparation of mixed metal oxide precursors for solid oxide fuel cells represents a very complex chemical process in which a metal may form oxides, hydroxides and various complex basic salts as intermediates. A detailed study to determine the relationship between synthesis strategies, morphology, sinteractivity and SOFC performance is a necessity. In this work, a direct relationship has been established between the precipitation agent, the calcination process, the final composition, particle sizes, sinterability and solid oxide fuel cell (SOFC) performance for nickel, copper and cobalt based anode materials. Nickel, copper and cobalt yttria stabilized zirconia (NiYSZ, CuYSZ and CoYSZ) anode materials were synthesized via hydrolysis of the corresponding chloride solutions with NH 3 , NH 3 + NaOH and NaOH as precipitation agents. The formation pathway was established for the various products by the direct observation of intermediate species throughout the synthesis process. A comparison of the powders indicates that the choice of precipitation agent greatly influences the final characteristics. The cobalt anodes offered the highest SOFC performance, while within each metal system, the anodes with a crystalline precursor resulted in higher exchange current densities for the charge transfer portion of the impedance spectra.
Respirators, medical masks, and barrier face coverings all filter airborne particles using similar physical principles. However, they are tested for certification using a variety of standardized test methods, creating challenges for the comparison of differently certified products. We have performed systematic experiments to quantify and understand the differences between standardized test methods for N95 respirators (NIOSH TEB-APR-STP-0059 under US 42 CFR 84), medical face masks (ASTM F2299/F2100), and COVID-19-related barrier face coverings (ASTM F3502-21). Our experiments demonstrate the role of face velocity, particle properties (mean size, size variability, electric charge, density, and shape), measurement techniques, and environmental preconditioning. The measured filtration efficiency was most sensitive to changes in face velocity and particle charge. Relative to the NIOSH method, users of the ASTM F2299/F2100 method have commonly used non-neutralized (highly charged) aerosols as well as smaller face velocities, each of which may result in approximately 10% higher measured filtration efficiencies. In the NIOSH method, environmental conditioning at elevated humidity increased filtration efficiency in some commercial samples while decreasing it in others, indicating that measurement should be performed both with and without conditioning. More generally, our results provide an experimental basis for the comparison of respirators certified under various international methods, including FFP2, KN95, P2, Korea 1st Class, and DS2.
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