Xing Huang

Influence of Functionalization of Nanocontainers on Self-Healing Anticorrosive Coatings

Feedback coating based on pH-induced release of inhibitor from organosilyl-functionalized containers is considered as a compelling candidate to achieve smart self-healing corrosion protection. Four key factors that determine the overall coating performance include (1) the uptake and release capacity of containers, (2) prevention of the premature leakage, (3) compatibility of containers in coating matrix, and (4) cost and procedure simplicity consideration. The critical influence introduced by organosilyl-functionalization of containers is systematically demonstrated by investigating MCM-41 silica nanoparticles modified with ethylenediamine (en), en-4-oxobutanoic acid salt (en-COO(-)), and en-triacetate (en-(COO(-))3) with higher and lower organic contents. The properties of the modified silica nanoparticles as containers were mainly characterized by solid-state (13)C nuclear magnetic resonance, scanning and transmission electron microscopy, N2 sorption, thermogravimetric analysis, small-angle X-ray scattering, dynamic light scattering, and UV-vis spectroscopy. Finally, the self-healing ability and anticorrosive performances of hybrid coatings were examined through scanning vibrating electrode technique (SVET) and electrochemical impedance spectroscopy (EIS). We found that en-(COO(-))3-type functionalization with content of only 0.23 mmol/g performed the best as a candidate for establishing pH-induced release system because the resulting capped and loaded (C-L) functionalized silica nanocontainers (FSNs) exhibit high loading (26 wt %) and release (80%) capacities for inhibitor, prevention of premature leakage (less than 2%), good dispersibility in coating matrix, and cost effectiveness.

Microwave Assisted Synthesis of Stable and Highly Active Ir-oxohydroxides for Electrochemical Oxidation of Water

Water splitting for hydrogen production in acidic media has been limited by the poor stability of the anodic electrocatalyst devoted to the oxygen evolution reaction (OER). To help circumvent this problem we have synthesized a class of novel Ir oxohydroxides by rapid microwave-asisted hydrothermal synthesis, which bridges the gap between electrodeposited amorphous IrOx films and crystalline IrO2 electrocatalysts prepared by calcination routes. For electrode loadings two orders of magnitude below current standards, the synthesized compounds present an unrivalled combination of high activity and stability under commercially relevant OER conditions in comparison to reported benchmarks, without need for pretreatment. The best compound achieved a lifetime 33 times longer than the best commercial Ir benchmark. Thus, the reported efficient synthesis of an Ir oxohydroxide phase with superior intrinsic OER performance constitutes a major step towards the targeted design of cost-efficient Ir based OER electrocatalysts for acidic media.

High-Performance Supported Iridium Oxohydroxide Water Oxidation Electrocatalysts

The synthesis of a highly active and yet stable electrocatalyst for the anodic oxygen evolution reaction (OER) remains a major challenge for acidic water splitting on an industrial scale. To address this challenge, we obtained an outstanding high-performance OER catalyst by loading Ir on conductive antimony-doped tin oxide (ATO)-nanoparticles by a microwave (MW)-assisted hydrothermal route. The obtained Ir phase was identified by using XRD as amorphous (XRD-amorphous), highly hydrated IrIII/IV oxohydroxide. To identify chemical and structural features responsible for the high activity and exceptional stability under acidic OER conditions with loadings as low as 20 μgIr  cm-2 , we used stepwise thermal treatment to gradually alter the XRD-amorphous Ir phase by dehydroxylation and crystallization of IrO2 . This resulted in dramatic depletion of OER performance, indicating that the outstanding electrocatalytic properties of the MW-produced IrIII/IV oxohydroxide are prominently linked to the nature of the produced Ir phase. This finding is in contrast with the often reported stable but poor OER performance of crystalline IrO2 -based compounds produced through more classical calcination routes. Our investigation demonstrates the immense potential of Ir oxohydroxide-based OER electrocatalysts for stable high-current water electrolysis under acidic conditions.

Bioinspired nanovalves with selective permeability and pH sensitivity

Biological systems with controlled permeability and release functionality, which are among the successful examples of living beings to survive in evolution, have attracted intensive investigation and have been mimicked due to their broad spectrum of applications. We present in this work, for the first time, an example of nuclear pore complexes (NPCs)-inspired controlled release system that exhibits on-demand release of angstrom-sized molecules. We do so in a cost-effective way by stabilizing porous cobalt basic carbonates as nanovalves and realizing pH-sensitive release of entrapped subnano cargo. The proof-of-concept work also consists of the establishment of two mathematical models to explain the selective permeability of the nanovalves. Finally, gram-sized (or larger) quantities of the bio-inspired controlled release system can be synthesized through a scaling-up strategy, which opens up opportunities for controlled release of functional molecules in wider practical applications.

Cobalt‐Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity

Abstract By taking inspiration from the catalytic properties of single‐site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon‐nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability.

A cost-effective pH-sensitive release system for water source pH detection

A facile and cost-effective strategy has been developed to form basic cobalt carbonate nanovalves at the orifice of mesoporous nanocontainers, which facilitate the pH sensitive release of functional cargo for up-scaling towards applications in water source pH detection.

In Situ Atomic-Scale Observation of Surface-Tension-Induced Structural Transformation of Ag-NiPx Core–Shell Nanocrystals

The properties of nanocrystals are highly dependent on their morphology, composition, and structure. Tailored synthesis over these parameters is successfully applied for the production of nanocrystals with desired properties for specific applications. However, in order to obtain full control over the properties, the behavior of nanocrystals under external stimuli and application conditions needs to be understood. Herein, using Ag-NiP x nanocrystals as a model system, we investigate the structural evolution upon thermal treatment by in situ aberration-corrected scanning transmission electron microscopy. A combination of real-time imaging with elemental analysis enables the observation of the transformation from a Ag-NiP x core-shell configuration to a Janus structure at the atomic scale. The transformation occurs through dewetting and crystallization of the NiP x shell and is accompanied by surface segregation of Ag. Further temperature increase leads to a complete sublimation of Ag and formation of individual Ni12P5 nanocrystals. The transformation is rationalized by theoretical modeling based on density functional theory calculations. Our model suggests that the transformation is driven by changes of the surface energy of NiP x and the interfacial energy between NiP x and Ag. The direct observation of atomistic dynamics during thermal-treatment-induced structural modification will help to understand more complex transformations that are induced by aging over time or the interaction with a reactive gas phase in applications such as catalysis.

In‐Situ Formation of Crystallographically‐Oriented Semiconductor Nanowire Arrays via Selective Vaporization

Mass production of high-quality semiconductor nanowire arrays (SNAs) with precisely controlled orientation and structure is essential for their application in nanoelectronics and optoelectronics. Here, we present a single-step approach for large-scale fabrication of [0001]-oriented SNAs via direct heating of their bulk components in a H2/Ar atmosphere. Real-time imaging during in-situ SEM experiments clearly demonstrates that the SNAs form through a selective vaporization process with respect to the crystallography of wurtzite crystals. We propose that the selective vaporization relies on the low symmetry of the wurtzite structure with large differences between surface energies of low-index planes. Further, we demonstrate that the approach can be extended to zinc-blende type structures through a cation exchange process. Finally, the high-quality of the SNAs is demonstrated by fabrication of photodetectors that present outstanding optoelectronic performances. We believe that our method represents a transformative new fabrication platform for large-scale fabrication of orientated SNAs with novel functionalities. Keywords: semiconductor nanowire arrays; wurtzite structure; selective vaporization