Search

MoS x serving as a hydrogen evolution reaction electrocatalyst is known for its morphology sensitive characteristic. The low temperature thermo-decomposition method provides an easy and energy saving pathway to produce highly active MoS x on carbon paper substrates. However, during the precursor solution drying process, the dynamics of liquid wetting behavior dominates the morphology of the precursor salt and eventually the morphology of MoS x . As a result, here, for the first time, by carefully pairing the substrate hydrophobicity and solvent polarity, the cohesive force between solvent molecules and adhesive force between solvent and carbon substrate can be tuned, and thus the MoS x morphology can be controlled. Pairing hydrophilic carbon paper with DMF + H2O mixing solvent results in a relatively strong adhesive force, as a result, we are able to lower the overpotential required at the benchmark current density, 10 mA/cm², to as low as 0.160 V and boost the current density to 40 mA/cm² at -+0.2 V vs RHE. This mainly results from the low charge transfer resistance and the well wrapped MoS x on carbon paper fiber structure. Furthermore, this well wrapped MoS x on hydrophilic carbon paper was proved to be comparably stable for constant voltage electrolysis operation. [ABSTRACT FROM AUTHOR]

Particle dispersions, such as pigment-based inks, comprise weakly bound, milled nanoparticles. The properties of these pigments depend on both their chemical composition and a rather complex structural hierarchy which emerges from these dispersions. The emergence of structure under semidilute conditions is related to the structure of the dilute particles, the particle spacing (mesh size), processing history and the interaction potential. Kinetic simulations could predict such emergence using these input parameters. In this paper, organic pigments are studied as an example of the importance of emergent structure to predict properties such as brilliance and opacity. Organic pigments are used to impart color to commercial inks, plastics, coatings and cosmetics. In many cases, dilute pigments are mass fractal structures consisting of aggregated nanoparticles held together by weak van der Waals forces. In water, surfactant is added to create a pigment dispersion (an ink). The final properties of a pigment emerge from a complex interplay between aggregation and dispersion of aggregates as a function of concentration. Samples of the organic pigment yellow 14, PY14, were milled to four primary particle sizes to study the effect on structural emergence. The interaction between surfactant-stabilized PY14 aggregates in an aqueous medium was quantified by the second virial coefficient, A2, which reflects long-range interactions. The degree of aggregation is associated with short-range attractive interactions between primary particles. In this series of pigments, the degree of aggregation increases dramatically with reduction in primary particle size. Concurrently, the second-order virial coefficient, A2, increases reflecting stronger long-range repulsive interactions with particle size. Structural emergence can be understood through the percolation concentration and the filler mesh size. A2 is translated into a repulsive interaction potential for use in dissipative particle dynamics simulations to enable predictive modeling. This description of the interactions between dispersed pigment aggregates allows for a more scientific and predictive approach to understand structural emergence. [ABSTRACT FROM AUTHOR]

The condition of negative surface tension of a binary regular solution is discussed in this paper using the recently reconfirmed Butler equation (Langmuir 2015, 31, 5796-5804). It is shown that the surface tension becomes negative only for solutions with strong repulsion between the components. This repulsion for negative surface tension should be so strong that this phenomenon appears only within a miscibility gap, that is, in a two-phase region of macroscopic liquid solutions. Thus, for a macroscopic solution, the negative surface tension is possible only in a nonequilibrium state. However, for a nano-solution, negative surface tension is also possible in equilibrium state. It is also shown that nano- and microemulsions can be thermodynamically stable against both coalescence and phase separation. Further, the thermodynamic theory of emulsion stability is developed for a three-component (A-B-C) system with A-rich droplets dispersed in a C-rich matrix, separated by the segregated B-rich layer (the solubility of B is limited in both A and C while the mutual solubility of A and C is neglected). It is shown that when a critical droplet size is achieved by forced emulsification, it is replaced by spontaneous emulsification and the droplet size is reduced further to its equilibrium value. The existence of maximum temperature of emulsion stability is shown. Using low-energy emulsification below this maximum temperature, spontaneous emulsification can appear, which is enhanced with further decrease of temperature. This finding can be applied to interpret the experimental observations on spontaneous emulsification or for the design of stable micro- and nanoemulsions. [ABSTRACT FROM AUTHOR]

The selection of viable conventional magnesium salts in electrolyte solutions for Mg secondary batteries is very limited. Reversible magnesium deposition was demonstrated with only MgTFSI2, in ethereal solutions. A recent report has suggested that Mg can be reversibly deposited from a solution of Mg(PF6)2 in tetrahydrofuran and acetonitrile. In this paper, we dispute that claim and show that PF6- anions passivate Mg anodes and completely inhibit any Mg deposition/dissolution process. We show that addition of chlorides suppresses the passivation phenomena and allows reversible Mg deposition/dissolution processes to commence. The Mg deposits have been examined via elemental analysis, scanning electron microscopy, and X-ray diffraction measurements, depicting a highly oriented, preferential Mg growth. This study evaluates the feasibility of employing PF6-based electrolytes for Mg batteries and exemplifies the aptitude of chlorides for suppressing passivation phenomena. [ABSTRACT FROM AUTHOR]

The increasing commercialization of consumer electronic products that make use of II-VI semiconductor quantum dots (QDs) has raised significant concerns about their impact on natural systems and human health once they are released into the environment at the end of the product's lifetime. In this paper, we demonstrate the addition of fluorescence lifetime spectroscopy to the existing tool kit of spectroscopic techniques to quantitatively monitor changes in QD properties as they form and degrade in solution. Our study reveals that because of its rich information content, fluorescence lifetime spectroscopy has a limited utility as a stand-alone technique in the study of QD formation and degradation. However, combining fluorescence lifetime spectroscopy with the commonly used emission quantum yield and peak width measurements along with other analytical methods, including ultraviolet-visible spectroscopy, transmission electron microscopy, and inductively coupled plasma mass spectrometry measurements, significantly enhances the existing analytical tool kit and provides the capability to monitor in real time, the formation and degradation of luminescent QDs in organic and aqueous solutions under environmentally relevant conditions. [ABSTRACT FROM AUTHOR]

Self-assembled monolayers (SAMs) have been widely employed as etching resists in wet lithography systems to form patterns in which the ordered molecular packing of the SAM regions significantly delays the etchant attack. A generally accepted recognition is that the SAMs ability to resist etching is positively correlated to the quality of the surface-assembled structures, and a more ordered molecular packing would correspond to a better etching resistance. Such a classical belief is debated in the present work by providing an alternative SAM-assisted negative lithography where ordered SAM regions are etched more quickly than their disordered counterparts. This method features a unique photoirradiation-imprinted patterning process that simply consists of two steps: (1) UV irradiation on an OH-terminated SAM-modified gold surface through a photomask and (2) the subsequent immersion of the exposed substrate in an aqueous etching solution of N-bromosuccinimide/pyridine to develop a wet lithographic pattern. The entire experimental process reveals a finding from previous work that the etching rate on the UV-exposed regions with disordered molecular packing could be modulated to be slower than that in the unexposed well-defined SAM regions. Longer irradiation times would also revert the patterns from negative to positive. Thus, by merely using one kind of SAM-modified surface to provide both positive and negative micropatterns on gold layers, one could obtain flexible opportunities for high-resolution micro/nanofabrication resembling photolithography. [ABSTRACT FROM AUTHOR]