Design Principles for Using Amphiphilic Polymers To Create Microporous Water.

Aqueous dispersions of microporous nanocrystals with dry, gas-accessible pores─referred to as "microporous water"─enable high densities of gas molecules to be transported through water. For many applications of microporous water, generalizable strategies are required to functionalize the external surface of microporous particles to control their dispersibility, stability, and interactions with other solution-phase components─including catalysts, proteins, and cells─while retaining as much of their internal pore volume as possible. Here, we establish design principles for the noncovalent surface functionalization of hydrophobic metal-organic frameworks with amphiphilic polymers that render the particles dispersible in water and enhance their hydrolytic stability. Specifically, we show that block co-polymers with persistence lengths that exceed the micropore aperture size of zeolitic imidazolate frameworks (ZIFs) can dramatically enhance ZIF particle dispersibility and stability while preserving porosity and >80% of the theoretical O2 carrying capacity. Moreover, enhancements in hydrolytic stability are greatest when the polymer can form strong bonds to exposed metal sites on the external particle surface. More broadly, our insights provide guidelines for controlling the interface between polymers and metal-organic framework particles in aqueous environments to augment the properties of microporous water.

Paper-based electrochromic glucose sensor with polyaniline on indium tin oxide nanoparticle layer as the optical readout.

Surging interests in point-of-care diagnostics have led to the development of many lightweight and cost-effective paper-based sensors. Particularly, sensors using colorimetric readouts are considered highly advantageous because no additional detector or device is required for signal display. Herein, we introduce an electrochemically operated colorimetric sensor that can compensate for the disadvantages of traditional colorimetry, hence enhancing response time, reusability and color uniformity. On a single paper substrate, carbon/graphite paste was screen printed to form the working and counter electrodes, and Ag/AgCl ink was applied for the reference electrode. Prussian blue and Glucose oxidase were employed on the one of the carbon electrodes for the detection of analytes, hydrogen peroxide and glucose. For the colorimetric readout, indium tin oxide nanoparticles and polyaniline were consecutively introduced on the other carbon electrode, which is used as the counter electrode. The color change of electrochromic polyaniline could be clearly observed, and its application as a colorimetric sensor was demonstrated by the quantitative analyses of hydrogen peroxide and glucose. This paper-based electrochromic glucose sensor showed a short response time of 30 s and exhibited a detection limit of 126 µM for glucose. Along with its rapid and easy detection by incorporating the merits of electrochemical sensing and colorimetry, the paper-based electrochromic sensor could potentially contribute to the development of point-of-care devices by combination with portable power sources.

Suppressing High-Current-Induced Phase Separation in Ni-Rich Layered Oxides by Electrochemically Manipulating Dynamic Lithium Distribution.

Understanding the cycling rate-dependent kinetics is crucial for managing the performance of batteries in high-power applications. Although high cycling rates may induce reaction heterogeneity and affect battery lifetime and capacity utilization, such phase transformation dynamics are poorly understood and uncontrollable. In this study, synchrotron-based operando X-ray diffraction is performed to monitor the high-current-induced phase transformation kinetics of LiNi0.6 Co0.2 Mn0.2 O2 . The sluggish Li diffusion at high Li content induces different phase transformations during charging and discharging, with strong phase separation and homogeneous phase transformation during charging and discharging, respectively. Moreover, by exploiting the dependence of Li diffusivity on the Li content and electrochemically tuning the initial Li content and distribution, phase separation pathway can be redirected to solid solution kinetics at a high charging rate of 7 C. Finite element analysis further elucidates the effect of the Li-content-dependent diffusion kinetics on the phase transformation pathway. The findings suggest a new direction for optimizing fast-cycling protocols based on the intrinsic properties of the materials.