RESUMO
Unraveling the catalyst surface structure and behavior during reactions is essential for both mechanistic understanding and performance optimization. Here we report a phenomenon of facet-dependent surface restructuring intrinsic to ß-Ni(OH)2 catalysts during oxygen evolution reaction (OER), discovered by the correlative ex situ and operando characterization. The ex situ study after OER reveals ß-Ni(OH)2 restructuring at the edge facets to form nanoporous Ni1-xO, which is Ni deficient containing Ni3+ species. Operando liquid transmission electron microscopy (TEM) and Raman spectroscopy further identify the active role of the intermediate ß-NiOOH phase in both the OER catalysis and Ni1-xO formation, pinpointing the complete surface restructuring pathway. Such surface restructuring is shown to effectively increase the exposed active sites, accelerate Ni oxidation kinetics, and optimize *OH intermediate bonding energy toward fast OER kinetics, which leads to an extraordinary activity enhancement of â¼16-fold. Facilitated by such a self-activation process, the specially prepared ß-Ni(OH)2 with larger edge facets exhibits a 470-fold current enhancement than that of the benchmark IrO2, demonstrating a promising way to optimize metal-(oxy)hydroxide-based catalysts.
RESUMO
Semiconducting metal oxides (SMOXs) are used widely for gas sensors. However, the effect of ambient humidity on the baseline and sensitivity of the chemiresistors is still a largely unsolved problem, reducing sensor accuracy and causing complications for sensor calibrations. Presented here is a general strategy to overcome water-sensitivity issues by coating SMOXs with a hydrophobic polymer separated by a metal-organic framework (MOF) layer that preserves the SMOX surface and serves a gas-selective function. Sensor devices using these nanoparticles display near-constant responses even when humidity is varied across a wide range [0-90 % relative humidity (RH)]. Furthermore, the sensor delivers notable performance below 20 % RH whereas other water-resistance strategies typically fail. Selectivity enhancement and humidity-independent sensitivity are concomitantly achieved using this approach. The reported tandem coating strategy is expected to be relevant for a wide range of SMOXs, leading to a new generation of gas sensors with excellent humidity-resistant performance.
RESUMO
Si-based electrodes offer exceptionally high capacity and energy density for lithium-ion batteries (LIBs),but suffer from poor structural stability and electrical conductivity that hamper their practical applications. To tackle these obstacles, we design a C/polymer bilayer coating deposited on Si-SiOx microparticles. The inner C coating is used to improve electrical conductivity. The outer C-nanoparticle-reinforced polypyrrole (CNP-PPy) is a polymer matrix composite that can minimize the volumetric expansion of Si-SiOx and enhance its structural stability during battery operation. Electrodes made of such robust Si-SiOx@C/CNP-PPy microparticles exhibit excellent cycling performance: 83% capacity retention (794 mAh g-1) at a 2 C rate after more than 900 cycles for a coin-type half cell, and 80% capacity retention (with initial energy density of 308 Wh kg-1) after over 1100 cycles for a pouch-type full cell. By comparing the samples with different coatings, an in-depth understanding of the performance enhancement is achieved, i.e., the C/CNP-PPy with cross-link bondings formed in the bilayer coating plays a key role for the improved structural stability. Moreover, a full battery using the Si-SiOx@C/CNP-PPy electrode successfully drives a car model, demonstrating a bright application prospect of the C/polymer bilayer coating strategy to make future commercial LIBs with high stability and energy density.