ABSTRACT
Polymer electrolyte membrane (PEM) electrolyzers are renewable energy storage systems that produce high purity hydrogen fuel from electrochemical water splitting. The PEM in particular is a key component that acts as a solid electrolyte between electrodes and separates the reactants, but despite these benefits, its internal ion transport mechanisms are not fully understood. Here, the first microfluidic PEM electrolyzer that is semi-transparent in the infrared (IR) spectrum is developed as a platform for characterizing the PEM hydration during operation. The electrochemical performance of the chip is compared to its PEM hydration, which is measured via synchrotron Fourier-transform infrared (FTIR) spectroscopy. The PEM water content is directly probed in the operating electrolyzer by measuring the transmitted light intensity at wavelengths around 10 µm. By supplying the electrolyzer with reactant starving flow rates, mass transport driven cell failure is provoked, which coincides with membrane dehydration. Furthermore, higher operating temperatures are observed to improve the stability in membrane hydration through increasing the membrane water uptake. The methods presented here prove the viability of IR techniques for characterizing membrane hydration, and future extension towards imaging and thermography would enable further quantitative studies of internal membrane transport behaviors.
ABSTRACT
Quantitative localization of metals in biological tissue sections is critical to obtain insight into metal toxicity mechanisms or their beneficial characteristics. This study presents the development of a quantitative LA-ICP MS bioimaging methodology based on the polymer film strategy and internal standardization. To maximize the number of elements mapped, an aqueous soluble polymer (dextran) was selected. Among the elements studied, the great majority (eight out eleven), i.e., Co, Ni, Cu, Zn, Se, Mo, Cd and Pt, exhibited linear regression after LA-ICP MS analysis of metal-spiked polymer standards. Methodology performances were carefully assessed as a function of the three internal standards (In, Rh and Ir) considered, the analytical operational conditions (ICP power, addition of O2 to ICP, and laser fluency) and the thickness of the biological tissue section. The results indicated that three groups (Co, Mo; Ni, Cu, Pt; and Zn, Se, Cd) of elements could be distinguished from their analytical response as a function of analytical conditions and the internal standard. These different element behaviors appeared to be mainly First Ionization Potential dependent (FIP). For elements with lower FIP (Co, Ni, Cu, Mo and Pt), differential responses due to carbon load in the ICP MS plasma could be efficiently corrected as a function of analytical conditions. Matrix effects were more pronounced for higher FIP elements (i.e., Zn, Cd and Se), and analysis of <10-µm thin sections without the addition of O2 to ICP MS plasma is recommended. LODs are in the range of 0.1-0.5 µg g-1 for Co, Mo, Cu, Ni, Pt and Cd as well as 0.9 and 1 µg g-1 for Zn and Se, respectively. The methodology was validated by means of a homemade metal-spiked kidney homogenate analyzed by LA-ICP MS imaging, and Co, Ni, Cu, Mo, and Pt provided the closest concentrations (5-29% bias) to the target values determined by ICP MS after mineralization. The methodology was applied to two types of clinical human samples undergoing different sample preparation protocols that did not affect internal standard homogeneity in the polymer film. This methodology is the first reported for the quantitative bioimaging of eight elements simultaneously.
Subject(s)
Lasers , Metals , Humans , Limit of Detection , Reference Standards , Spectrum AnalysisABSTRACT
Relaxors are very interesting materials but most of the time they are restricted to perovskite materials and thus their flexibility is limited. We have previously shown that tetragonal tungsten bronze (TTB) niobate Ba(2)PrFeNb(4)O(15) was a relaxor below 170 K and that Ba(2)NdFeNb(4)O(15) displays a ferroelectric behavior with a T(C) = 323 K. On scanning the whole solid solution Ba(2)Pr(x)Nd(1-x)FeNb(4)O(15) (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8 and 1), we demonstrate here a continuous crossover between these end member behaviors with a coexistence of ferroelectricity and relaxor in the intermediate range. This tunability is ascribed to the peculiar structure of the TTB networks which is more open than the classical perovskites. This allows for the coexistence of long range and short range orders and thus opens up the range of relaxor materials.
