Zewei Wang

Hairy Uniform Permanently Ligated Hollow Nanoparticles with Precise Dimension Control and Tunable Optical Properties

The ability to tailor the size and shape of nanoparticles (NPs) enables the investigation into the correlation between these parameters and optical, optoelectronic, electrical, magnetic, and catalytic properties. Despite several effective approaches available to synthesize NPs with a hollow interior, it remains challenging to have a general strategy for creating a wide diversity of high-quality hollow NPs with different dimensions and compositions on demand. Herein, we report on a general and robust strategy to in situ crafting of monodisperse hairy hollow noble metal NPs by capitalizing on rationally designed amphiphilic star-like triblock copolymers as nanoreactors. The intermediate blocks of star-like triblock copolymers can associate with metal precursors via strong interaction (i.e., direct coordination or electrostatic interaction), followed by reduction to yield hollow noble metal NPs. Notably, the outer blocks of star-like triblock copolymers function as ligands that intimately and permanently passivate the surface of hollow noble metal NPs (i.e., forming hairy permanently ligated hollow NPs with superior solubility in nonpolar solvents). More importantly, the diameter of the hollow interior and the thickness of the shell of NPs can be readily controlled. As such, the dimension-dependent optical properties of hollow NPs are scrutinized by combining experimental studies and theoretical modeling. The dye encapsulation/release studies indicated that hollow NPs may be utilized as attractive guest molecule nanocarriers. As the diversity of precursors are amenable to this star-like triblock copolymer nanoreactor strategy, it can conceptually be extended to produce a rich variety of hairy hollow NPs with different dimensions and functionalities for applications in catalysis, water purification, optical devices, lightweight fillers, and energy conversion and storage.

Light-enabled reversible self-assembly and tunable optical properties of stable hairy nanoparticles

Significance This work reports a versatile and robust strategy for creating monodisperse plasmonic nanoparticles (NPs) intimately and permanently capped with photoresponsive polymers via capitalizing on amphiphilic star-like diblock copolymer nanoreactors. The reversibly assembled nanostructures comprising photoresponsive NPs may exhibit a broad range of new attributes, functions, and applications as a direct consequence of size-dependent physical property from individual NP and the collective property originated from the NP interaction due to their close proximity within nanostructure. The ability to dynamically organize functional nanoparticles (NPs) via the use of environmental triggers (temperature, pH, light, or solvent polarity) opens up important perspectives for rapid and convenient construction of a rich variety of complex assemblies and materials with new structures and functionalities. Here, we report an unconventional strategy for crafting stable hairy NPs with light-enabled reversible and reliable self-assembly and tunable optical properties. Central to our strategy is to judiciously design amphiphilic star-like diblock copolymers comprising inner hydrophilic blocks and outer hydrophobic photoresponsive blocks as nanoreactors to direct the synthesis of monodisperse plasmonic NPs intimately and permanently capped with photoresponsive polymers. The size and shape of hairy NPs can be precisely tailored by modulating the length of inner hydrophilic block of star-like diblock copolymers. The perpetual anchoring of photoresponsive polymers on the NP surface renders the attractive feature of self-assembly and disassembly of NPs on demand using light of different wavelengths, as revealed by tunable surface plasmon resonance absorption of NPs and the reversible transformation of NPs between their dispersed and aggregated states. The dye encapsulation/release studies manifested that such photoresponsive NPs may be exploited as smart guest molecule nanocarriers. By extension, the star-like block copolymer strategy enables the crafting of a family of stable stimuli-responsive NPs (e.g., temperature- or pH-sensitive polymer-capped magnetic, ferroelectric, upconversion, or semiconducting NPs) and their assemblies for fundamental research in self-assembly and crystallization kinetics of NPs as well as potential applications in optics, optoelectronics, magnetic technologies, sensory materials and devices, catalysis, nanotechnology, and biotechnology.

Explosive shock processing of Pr2Fe14B/α-Fe exchange-coupled nanocomposite bulk magnets

Explosive shock compaction was used to consolidate powders obtained from melt-spun Pr2Fe14B/–Fe nanocomposite ribbons, to produce fully dense cylindrical compacts of 17–41-mm diameter and 120-mm length. Characterization of the compacts revealed refinement of the nanocomposite structure, with approximately 15 nm uniformly sized grains. The compact produced at a shock pressure of approximately 1 GPa maintained a high coercivity, and its remanent magnetization and maximum energy product were measured to be 0.98 T and 142 kJ/m 3 , respectively. The compact produced at 4–7 GPa showed a decrease in magnetic properties while that made at 12 GPa showed a magnetic softening behavior. However, in both of these cases, a smooth hysteresis loop implying exchange coupling and a coercivity of 533 kA/m were fully recovered after heat treatment. The results illustrate that the explosive compaction followed by post-shock heat treatment can be used to fabricate exchange-coupled nanocomposite bulk magnets with optimized magnetic properties.

Shock Compression of FePt and FePt/Fe3Pt Nanoparticles: Exchange‐Coupled Nanocomposite Magnets

The shock‐compression response of partially‐ordered 10–20 nm size FePt and FePt/Fe3Pt nanocomposite particles has been studied in this work. The chemically synthesized and annealed nanoparticle powders were packed into three‐capsule plate‐impact fixtures at ∼45% density and shock consolidated using a gas‐gun at impact velocities of 500 and 750 m/s. The compacts were recovered as disc‐shaped bulk magnets, with up to ∼90% higher density than the initial packing density. Transmission electron microscopy analysis revealed plastic deformation and flow of nanoparticles in the process of void annihilation and densification. High‐resolution imaging revealed complete retention of nano‐size of particles in the dense magnets. Shock compression of the FePt nanoparticles also resulted in an order‐to‐disorder phase transition from fct‐to‐fcc structure. However, annealing at temperatures around 700°C caused complete reversal and formation of ordered fct structure. The resulting magnetic property measurements showed ener...

All-Inorganic Perovskite Nanocrystals with a Stellar Set of Stabilities and Their Use in White Light-Emitting Diodes

We report a simple, robust, and inexpensive strategy to enable all-inorganic CsPbX3 perovskite nanocrystals (NCs) with a set of markedly improved stabilities, that is, water stability, compositional stability, phase stability, and phase segregation stability via impregnating them in solid organic salt matrices (i.e., metal stearate; MSt). In addition to acting as matrices, MSt also functions as the ligand bound to the surface of CsPbX3 NCs, thereby eliminating the potential damage of NCs commonly encountered during purification as in copious past work. Quite intriguingly, the resulting CsPbX3-MSt nanocomposites display an outstanding suite of stabilities. First, they retain high emission in the presence of water because of the insolubility of MSt in water, signifying their excellent water stability. Second, anion exchange between CsPbBr3-MSt and CsPbI3-MSt nanocomposites is greatly suppressed. This can be ascribed to the efficient coating of MSt, thus effectively isolating the contact between CsPbBr3 and CsPbI3 NCs, reflecting notable compositional stability. Third, remarkably, after being impregnated by MSt, the resulting CsPbI3-MSt nanocomposites sustain the cubic phase of CsPbI3 and high emission, manifesting the strikingly improved phase stability. Finally, phase segregation of CsPbBr1.5I1.5 NCs is arrested via the MSt encapsulation (i.e., no formation of the respective CsPbBr3 and CsPbI3), thus rendering pure and stable photoluminescence (i.e., demonstration of phase segregation stability). Notably, when assembled into typical white light-emitting diode architecture, CsPbBr1.5I1.5-MSt nanocomposites exhibit appealing performance, including a high color rendering index ( Ra) and a low color temperature ( Tc). As such, the judicious encapsulation of perovskite NCs into organic salts represents a facile and robust strategy for creating high-quality solid-state luminophores for use in optoelectronic devices.

Shock Compaction of Exchange‐Coupled Nanocomposite Magnetic Powders

Shock compaction was used to consolidate exchange‐coupled R2Fe14B/α‐Fe (R=Nd, Pr) hard/soft phase nanocomposite powders using a three‐capsule plate‐impact gas‐gun loading system. Design of the consolidation fixture, densification conditions, and starting powder properties allowed control of the final density and microstructure of the shock‐compacted samples. Highly dense compacts (∼99% of full density) with minimal interparticle melted/re‐solidified zones and free from macrocracks were obtained under optimum consolidation conditions, in which case a laminar microstructure of the ribbon‐shaped powders was observed. TEM characterization revealed complete retention of the nanostructure of the hard and soft phases, which grain sizes were within 20–25 nm in the final shock‐compacted composite magnets. Retention of nanostructure ensured exchange coupling between the hard and soft phases, resulting in magnetic properties in the shock consolidated compacts similar to those of starting powders.