Jingshan S. Du

Intermetallic Nanocrystals: Syntheses and Catalytic Applications

At the forefront of nanochemistry, there exists a research endeavor centered around intermetallic nanocrystals, which are unique in terms of long-range atomic ordering, well-defined stoichiometry, and controlled crystal structure. In contrast to alloy nanocrystals with no elemental ordering, it is challenging to synthesize intermetallic nanocrystals with a tight control over their size and shape. Here, recent progress in the synthesis of intermetallic nanocrystals with controllable sizes and well-defined shapes is highlighted. A simple analysis and some insights key to the selection of experimental conditions for generating intermetallic nanocrystals are presented, followed by examples to highlight the viable use of intermetallic nanocrystals as electrocatalysts or catalysts for various reactions, with a focus on the enhanced performance relative to their alloy counterparts that lack elemental ordering. Within the conclusion, perspectives on future developments in the context of synthetic control, structure-property relationships, and applications are discussed.

Embedding Ultrafine and High-Content Pt Nanoparticles at Ceria Surface for Enhanced Thermal Stability

Ultrafine Pt nanoparticles loaded on ceria (CeO2) are promising nanostructured catalysts for many important reactions. However, such catalysts often suffer from thermal instability due to coarsening of Pt nanoparticles at elevated temperatures, especially for those with high Pt loading, which leads to severe deterioration of catalytic performances. Here, a facile strategy is developed to improve the thermal stability of ultrafine (1–2 nm)‐Pt/CeO2 catalysts with high Pt content (≈14 wt%) by partially embedding Pt nanoparticles at the surface of CeO2 through the redox reaction at the solid–solution interface. Ex situ heating studies demonstrate the significant increase in thermal stability of such embedded nanostructures compared to the conventional loaded catalysts. The microscopic pathways for interparticle coarsening of Pt embedded or loaded on CeO2 are further investigated by in situ electron microscopy at elevated temperatures. Their morphology and size evolution with heating temperature indicate that migration and coalescence of Pt nanoparticles are remarkably suppressed in the embedded structure up to about 450 °C, which may account for the improved thermal stability compared to the conventional loaded structure.

Structural Evolution of Three-Component Nanoparticles in Polymer Nanoreactors

Recent developments in scanning probe block copolymer lithography (SPBCL) enable the confinement of multiple metal precursors in a polymer nanoreactor and their subsequent transformation into a single multimetallic heterostructured nanoparticle through thermal annealing. However, the process by which multimetallic nanoparticles form in SPBCL-patterned nanoreactors remains unclear. Here, we utilize the combination of PEO-b-P2VP and Au, Ag, and Cu salts as a model three-component system to investigate this process. The data suggest that the formation of single-component Au, Ag, or Cu nanoparticles within polymer nanoreactors consists of two stages: (I) nucleation, growth, and coarsening of the particles to yield a single particle in each reactor; (II) continued particle growth by depletion of the remaining precursor in the reactor until the particle reaches a stable size. Also, different aggregation rates are observed for single-component particle formation (Au > Ag > Cu). This behavior is also observed for two-component systems, where nucleation sites have greater Au content than the other metals. This information can be used to trap nanoparticles with kinetic structures. High-temperature treatment ultimately facilitates the structural evolution of the kinetic particle into a particle with a fixed structure. Therefore, with multicomponent systems, a third stage that involves elemental redistribution within the particle must be part of the description of the synthetic process. This work not only provides a glimpse at the mechanism underlying multicomponent nanoparticle formation in SPBCL-generated nanoreactors but also illustrates, for the first time, the utility of SPBCL as a platform for controlling the architectural evolution of multimetallic nanoparticles in general.

Facile synthesis of high-quality Pt nanostructures with a controlled aspect ratio for methanol electro-oxidation

High-quality Pt nanobars with a controlled aspect ratio were synthesized by varying the amount of formaldehyde in benzyl alcohol containing oleylamine and exhibited substantially enhanced electrocatalytic properties for methanol oxidation relative to the commercial Pt/C.

Solution-Phase Photochemical Nanopatterning Enabled by High-Refractive-Index Beam Pen Arrays

A high-throughput, solution-based, scanning-probe photochemical nanopatterning approach, which does not require the use of probes with subwavelength apertures, is reported. Specifically, pyramid arrays made from high-refractive-index polymeric materials were constructed and studied as patterning tools in a conventional liquid-phase beam pen lithography experiment. Two versions of the arrays were explored with either metal-coated or metal-free tips. Importantly, light can be channeled through both types of tips and the appropriate solution phase (e.g., H2O or CH3OH) and focused on subwavelength regions of a substrate to effect a photoreaction in solution that results in localized patterning of a self-assembled monolayer (SAM)-coated Au thin film substrate. Arrays with as many as 4500 pyramid-shaped probes were used to simultaneously initiate thousands of localized free-radical photoreactions (decomposition of a lithium acylphosphinate photoinitiator in an aqueous solution) that result in oxidative removal of the SAM. The technique is attractive since it allows one to rapidly generate features less than 200 nm in diameter, and the metal-free tips afford more than 10-fold higher intensity than the tips with nanoapertures over a micrometer propagation length. In principle, this mask-free method can be utilized as a versatile tool for performing a wide variety of photochemistries across multiple scales that may be important in high-throughput combinatorial screening applications related to chemistry, biology, and materials science.

The Structural Fate of Individual Multicomponent Metal-Oxide Nanoparticles in Polymer Nanoreactors

Multicomponent nanoparticles can be synthesized with either homogeneous or phase-segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal-oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized by using scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co-Ni-O system forms a rock salt structure largely owing to the miscibility of CoO and NiO, while Cu-Ni-O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher-ordered structure, Co-Ni-Cu-O, was found to follow the behavior of lower ordered systems.

Windowless Observation of Evaporation-Induced Coarsening of Au–Pt Nanoparticles in Polymer Nanoreactors

The interactions between nanoparticles and solvents play a critical role in the formation of complex, metastable nanostructures. However, direct observation of such interactions with high spatial and temporal resolution is challenging with conventional liquid-cell transmission electron microscopy (TEM) experiments. Here, a windowless system consisting of polymer nanoreactors deposited via scanning probe block copolymer lithography (SPBCL) on an amorphous carbon film is used to investigate the coarsening of ultrafine (1-3 nm) Au-Pt bimetallic nanoparticles as a function of solvent evaporation. In such reactors, homogeneous Au-Pt nanoparticles are synthesized from metal-ion precursors in situ under electron irradiation. The nonuniform evaporation of the thin polymer film not only concentrates the nanoparticles but also accelerates the coalescence kinetics at the receding polymer edges. Qualitative analysis of the particle forces influencing coalescence suggests that capillary dragging by the polymer edges plays a significant role in accelerating this process. Taken together, this work (1) provides fundamental insight into the role of solvents in the chemistry and coarsening behavior of nanoparticles during the synthesis of polyelemental nanostructures, (2) provides insight into how particles form via the SPBCL process, and (3) shows how SPBCL-generated domes, instead of liquid cells, can be used to study nanoparticle formation. More generally, it shows why conventional models of particle coarsening, which do not take into account solvent evaporation, cannot be used to describe what is occurring in thin film, liquid-based syntheses of nanostructures.

Using STEM to Probe the in-situ Dynamics of Multimetallic Nanoparticles Grown in Polymer Nanoreactors

Although there has been much progress, the dynamics of nanoparticle (NP) growth in liquids and the nature of liquid-particle interactions during the growth process are poorly understood. This is especially true when studying the evolution of multimetallic NPs in liquid environments or polymer matrices [1]. The growth trajectory of NPs and several inter-particle dynamic phenomena, such as Ostwald ripening, migration-coalescence, and oriented attachment, have been observed using liquid-cell in-situ (scanning) transmission electron microscopy [(S)TEM] techniques [2,3]. Evaporation or decomposition of a dispersant thin film on a surface can drive NPs either to self-assemble into 2D monolayers and complicated nanopatterns, or to coarsen and form islands and thin solid films. This evaporation-driven material deposition is often spatially nonuniform at the nanometer scale [4]. The formation process and kinetics of such nonuniformity at the nanoscale have been difficult to directly monitor, since imaging such interactions by in-situ electron microscopy often suffers from the low contrast and fast evaporation of most liquids. Polymer nanoreactors made by Dip-Pen Nanolithography (DPN) have been proven to be a powerful emerging approach to control the formation of multimetallic NPs by thermally driven growth and coarsening [5]. Due to the high decomposition temperature, polymer nanoreactors have also provided a relatively stable fluidic environment to study NP dynamics using STEM [6] (Figure 1A). Herein, we report a study focused on the growth of Au-Pt NPs and their coarsening kinetics driven by polymer decomposition. The process is followed by in-situ STEM on thin sections of polymer nanoreactors, which are patterned on electron-transparent amorphous carbon films.