Zhaoliang Zheng

Silica/Polymer Double-Walled Hybrid Nanotubes: Synthesis and Application as Stimuli-Responsive Nanocontainers in Self-Healing Coatings

We report the development of silica/polymer double-walled hybrid nanotubes, which consist of a hollow cavity, a porous silica inner wall, and a stimuli-responsive (pH, temperature, and redox) polymeric outer wall, as a novel nanocontainer system. The length, diameter, wall thickness, and aspect ratio of the hybrid nanotubes are precisely controlled in the range of 48-506 nm, 41-68 nm, 3-24 nm, and 1.2-7.6, respectively. The hybrid nanotubes loaded with active molecules exhibit morphology-dependent release and pH-, temperature-, redox-responsive release, which enable a wide range of applications from energy storage to drug delivery and self-healing coatings for metal corrosion protection.

Progressive release of a palladium-pyridyl complex from a layer-by-layer multilayer and illustrative application to catalytic Suzuki coupling

Quartz slides bearing layers of a palladium azopyridine complex are seen to liberate catalytic amounts of a soluble active palladium species which can be used for Suzuki coupling.

An efficient and reusable silica/dendrimer supported platinum catalyst for electron transfer reactions

A series of Pt nanoparticles (NPs) smaller than 3 nm were successfully encapsulated in dendrimer/SBA-15 organic and inorganic hybrid composite. The obtained catalysts were characterized by XPS, XRD and TEM. The results of XPS and XRD indicate the existence of Pt NPs in the hybrid matrix. TEM images display the Pt NPs with narrow size distribution are monodispersed in SBA-15 channels. Catalytic property of the supported Pt catalysts was investigated in inorganic (ferricyanide to ferrocyanide by thiosulfate) and organic (p-nitrophenol to p-aminophenol by sodium borohydride) electron transfer (redox) reactions. In both cases, the reduction reactions followed smoothly and the catalysts showed excellent catalytic activity. Moreover, the catalysts can be easily separated and reused several times preserving good catalytic performance.

Bifunctional composite prepared using layer-by-layer assembly of polyelectrolyte – gold nanoparticle films on Fe3O4 – silica core–shell microspheres

Layer-by-layer assembly of polyelectrolyte–gold nanoparticles (NPs) multilayer films on Fe3O4–silica core–shell microspheres provides a convenient method to design a bifunctional hybrid composite combining the catalytic and magnetic performance together. The Au NPs are effectively immobilized in the polyelectrolyte layer without blocking the catalytic sites. The obtained hybrid magnetic microspheres exhibit high catalytic performance in both organic and inorganic reduction reactions. The use of magnetic support for the immobilization of Au NPs guarantees facile, clean, fast and efficient separation of the catalyst at the end of the reaction cycle.

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.

Highly Stable and Conductive Microcapsules for Enhancement of Joule Heating Performance

Nanocarbons show great promise for establishing the next generation of Joule heating systems, but suffer from the limited maximum temperature due to precociously convective heat dissipation from electrothermal system to surrounding environment. Here we introduce a strategy to eliminate such convective heat transfer by inserting highly stable and conductive microcapsules into the electrothermal structures. The microcapsule is composed of encapsulated long-chain alkanes and graphene oxide/carbon nanotube hybrids as core and shell material, respectively. Multiform carbon nanotubes in the microspheres stabilize the capsule shell to resist volume-change-induced rupture during repeated heating/cooling process, and meanwhile enhance the thermal conductance of encapsulated alkanes which facilitates an expeditious heat exchange. The resulting microcapsules can be homogeneously incorporated in the nanocarbon-based electrothermal structures. At a dopant of 5%, the working temperature can be enhanced by 30% even at a low voltage and moderate temperature, which indicates a great value in daily household applications. Therefore, the stable and conductive microcapsule may serve as a versatile and valuable dopant for varieties of heat generation systems.

Microencapsulated Phase Change Materials in Solar-Thermal Conversion Systems: Understanding Geometry-Dependent Heating Efficiency and System Reliability

The performance of solar-thermal conversion systems can be improved by incorporation of nanocarbon-stabilized microencapsulated phase change materials (MPCMs). The geometry of MPCMs in the microcapsules plays an important role for improving their heating efficiency and reliability. Yet few efforts have been made to critically examine the formation mechanism of different geometries and their effect on MPCMs-shell interaction. Herein, through changing the cooling rate of original emulsions, we acquire MPCMs within the nanocarbon microcapsules with a hollow structure of MPCMs (h-MPCMs) or solid PCM core particles (s-MPCMs). X-ray photoelectron spectroscopy and atomic force microscopy reveals that the capsule shell of the h-MPCMs is enriched with nanocarbons and has a greater MPCMs-shell interaction compared to s-MPCMs. This results in the h-MPCMs being more stable and having greater heat diffusivity within and above the phase transition range than the s-MPCMs do. The geometry-dependent heating efficiency and system stability may have important and general implications for the fundamental understanding of microencapsulation and wider breadth of heating generating systems.

Oriented cell division affects the global stress and cell packing geometry of a monolayer under stretch

Cell division plays a vital role in tissue morphogenesis and homeostasis, and the division plane is crucial for cell fate. For isolated cells, extensive studies show that the orientation of divisions is sensitive to cell shape and the direction of extrinsic mechanical forces. However, it is poorly understood that how the cell divides within a cell monolayer and how the local stress change, due to the division, affects the global stress of epithelial monolayers. Here, we use the vertex dynamics models to investigate the effects of division orientation on the configurations and mechanics of a cell monolayer under stretch. We examine three scenarios of the divisions: dividing along the stretch axis, dividing along the geometric long axis of cells, and dividing at a random angle. It is found that the division along the long cell axis can induce the minimal energy difference, and the global stress of the monolayer after stretch releases more rapidly in this case. Moreover, the long-axis division can result in more random cell orientations and more isotropic cell shapes within the monolayer, comparing with other two cases. This study helps understand the division orientation of cells within a monolayer under mechanical stimuli, and may shed light on linking individual cells behaviors to the global mechanics and patterns of tissues.

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.

Controlled Synthesis of Noble Metallic Dimers and the Influence of Secondary Metals on the Catalytic Activity

To precisely discuss the influence of secondary metals on the whole nanosystem, two different types of Pd/Au dimers are constructed by reducing Au precursors with or without ascorbic acid. The number and size of gold nanoparticles attaching on larger Pd nanocrystals can be roughly controlled. Furthermore, based on electrocatalysis, we find that multidecorated dimers are generally more active than singly decorated ones. Meanwhile, the amount of Au precursor used in preparing multidecorated dimers is found to be very important to the catalytic activity of the as-prepared catalysts. The performance of the catalyst is enhanced with the increasing of Au precursor when the Au/Pd molar ratio is below 1:4, but hindered when the ratio climbs higher. Finally, this work provides a promising approach in forming hybrid nanocompositions to find an optimized amount of secondary metal, which is of significance in academic and economic fields.