Yujie Xiong

Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. Our aim is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Finally, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Omnidirectional printing of flexible, stretchable, and spanning silver microelectrodes.

Flexible, stretchable, and spanning microelectrodes that carry signals from one circuit element to another are needed for many emerging forms of electronic and optoelectronic devices. We have patterned silver microelectrodes by omnidirectional printing of concentrated nanoparticle inks in both uniform and high–aspect ratio motifs with minimum widths of approximately 2 micrometers onto semiconductor, plastic, and glass substrates. The patterned microelectrodes can withstand repeated bending and stretching to large levels of strain with minimal degradation of their electrical properties. With this approach, wire bonding to fragile three-dimensional devices and spanning interconnects for solar cell and light-emitting diode arrays are demonstrated.

Printed Assemblies of Inorganic Light-Emitting Diodes for Deformable and Semitransparent Displays

Bend Me, Stretch Me In the push toward flexible electronics, much research has focused on using organic conducting materials, including light-emitting diodes (LEDs), because they are more readily processed using scalable techniques. Park et al. (p. 977) have developed a series of techniques for depositing and assembling inorganic LEDs onto glass, plastic, or rubber. Conventional processing techniques are used to connect the LEDs in order to create flexible, stretchable displays, which, because the active diode material only covers a small part of the substrate, are mostly transparent. Methods to fabricate and assemble inorganic light-emitting diodes provide a route toward transparent, flexible, or stretchable display devices. We have developed methods for creating microscale inorganic light-emitting diodes (LEDs) and for assembling and interconnecting them into unusual display and lighting systems. The LEDs use specialized epitaxial semiconductor layers that allow delineation and release of large collections of ultrathin devices. Diverse shapes are possible, with dimensions from micrometers to millimeters, in either flat or “wavy” configurations. Printing-based assembly methods can deposit these devices on substrates of glass, plastic, or rubber, in arbitrary spatial layouts and over areas that can be much larger than those of the growth wafer. The thin geometries of these LEDs enable them to be interconnected by conventional planar processing techniques. Displays, lighting elements, and related systems formed in this manner can offer interesting mechanical and optical properties.

From Bimetallic Metal‐Organic Framework to Porous Carbon: High Surface Area and Multicomponent Active Dopants for Excellent Electrocatalysis

Bimetallic metal-organic frameworks are rationally synthesized as templates and employed for porous carbons with retained morphology, high graphitization degree, hierarchical porosity, high surface area, CoNx moiety and uniform N/Co dopant by pyrolysis. The optimized carbon with additional phosphorus dopant exhibits excellent electrocatalytic performance for the oxygen reduction reaction, which is much better than the benchmark Pt/C in alkaline media.

Shape-Controlled Synthesis of Pd Nanocrystals and Their Catalytic Applications

Palladium is a marvelous catalyst for a rich variety of reactions in industrial processes and commercial devices. Most Pd-catalyzed reactions exhibit structure sensitivity, meaning that the activity or selectivity depends on the arrangement of atoms on the surface. Previously, such reactions could only be studied in ultrahigh vacuum using Pd single crystals cut with a specific crystallographic plane. However, these model catalysts are far different from real catalytic systems owing to the absence of atoms at corners and edges and the extremely small specific surface areas for the model systems. Indeed, enhancing the performance of a Pd-based catalyst, in part to reduce the amount needed of this precious and rare metal for a given reaction, requires the use of Pd with the highest possible specific surface area. Recent advances in nanocrystal synthesis are offering a great opportunity to investigate and quantify the structural sensitivity of catalysts based on Pd and other metals. For a structure-sensitive reaction, the catalytic properties of Pd nanocrystals are strongly dependent on both the size and shape. The shape plays a more significant role in controlling activity and selectivity, because the shape controls not only the facets but also the proportions of surface atoms at corners, edges, and planes, which affect the outcomes of possible reactions. We expect catalysts based on Pd nanocrystals with optimized shapes to meet the increasing demands of industrial applications at reduced loadings and costs. In this Account, we discuss recent advances in the synthesis of Pd nanocrystals with controlled shapes and their resulting performance as catalysts for a large number of reactions. First, we review various synthetic strategies based on oxidative etching, surface capping, and kinetic control that have been used to direct the shapes of nanocrystals. When crystal growth is under thermodynamic control, the capping agent plays a pivotal role in determining the shape of a product by altering the order of surface energies for different facets through selective adsorption; the resulting product has the lowest possible total surface energy. In contrast, the product of a kinetically controlled synthesis often deviates from the thermodynamically favored structure, with notable examples including nanocrystals enclosed by high-index facets or concave surfaces. We then discuss the key parameters that control the nucleation and growth of Pd nanocrystals to decipher potential growth mechanisms and build a connection between the experimental conditions and the pathways to different shapes. Finally, we present a number of examples to highlight the use of these Pd nanocrystals as catalysts or electrocatalysts for various applications with structure-sensitive properties. We believe that a deep understanding of the shape-dependent catalytic properties, together with an ability to experimentally maneuver the shape of metal nanocrystals, will eventually lead to rational design of advanced catalysts with substantially enhanced performance.

Surface Polarization Matters: Enhancing the Hydrogen-Evolution Reaction by Shrinking Pt Shells in Pt–Pd–Graphene Stack Structures†

Surface charge state plays an important role in tuning the catalytic performance of nanocrystals in various reactions. Herein, we report a synthetic approach to unique Pt-Pd-graphene stack structures with controllable Pt shell thickness. These unique hybrid structures allow us to correlate the Pt thickness with performance in the hydrogen-evolution reaction (HER). The HER activity increases with a decrease in the Pt thickness, which is well explained by surface polarization mechanism as suggested by first-principles simulations. In this hybrid system, the difference in work functions of Pt and Pd results in surface polarization on the Pt surface, tuning its charge state for hydrogen reduction. Meanwhile, the supporting graphene provides two-dimensional channels for efficient charge transport, improving the HER activities. This work opens up possibilities of reducing Pt usage while achieving high HER performance.

Chemically exfoliated metallic MoS2 nanosheets: A promising supporting co-catalyst for enhancing the photocatalytic performance of TiO2 nanocrystals

AbstractElectron-hole separation is a critical step to achieving efficient photocatalysis, towards which use of co-catalysts has become a widely used strategy. Despite the tremendous efforts and demonstrated functions of noble metal co-catalysts, seeking noble metal-free co-catalysts will always be the goal when designing cost-effective, high-performance hybrid photocatalysts. In this work, we demonstrate that MoS2 nanosheets with 1T phase (i.e., octahedral phase) can function as a co-catalyst with multiple merits: (1) Noble-metal-free; (2) high mobility for charge transport; (3) high density of active sites for H2 evolution on basal planes; (4) good performance stability; (5) high light transparency. As demonstrated in both photocatalytic hydrogen production and Rhodamine B degradation, the developed hybrid structure with TiO2 exhibits excellent performance, in sharp contrast to bare TiO2 and the hybrid counterpart with 2H-MoS2.

Synthesis of silver nanoplates at high yields by slowing down the polyol reduction of silver nitrate with polyacrylamide

This communication describes a simple route to Ag nanoplates by slowing the polyol reduction of silver nitrate with polyacrylamide (PAM). In addition to its role as a stabilizer for Ag colloids, the amino groups of PAM can form complexes with Ag+ ions in the solution to substantially reducing the reduction rate, leading to the formation of thin nanoplates.

Synthesis of rod-, twinrod-, and tetrapod-shaped CdS nanocrystals using a highly oriented solvothermal recrystallization technique

Rod-, twinrod- and tetrapod-shaped CdS nanocrystals have been successfully prepared from the starting spherical CdS nanocrystals via a highly oriented solvothermal recrystallization technique. X-Ray powder diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy have been used to characterize the crystal structure and growth direction of the obtained sample. The present technique may open a new doorway to one-dimensional nanosized semiconductors from the same kind of materials with irregular shape or larger size.

Integration of an Inorganic Semiconductor with a Metal–Organic Framework: A Platform for Enhanced Gaseous Photocatalytic Reactions

Ultrafast spectroscopy demonstrates that charge transfer can occur between photoexcited inorganic semiconductors and metal-organic frameworks (MOFs), supplying long-lifetime electrons for the reduction of gas molecules adsorbed on the MOF. As a proof of concept, a unique method is developed for synthesizing Cu3 (BTC)2 @TiO2 core-shell structures with macroporous semiconductor shells that allow gas molecules to be captured in the cores.