Rongchao Jin

Controlling anisotropic nanoparticle growth through plasmon excitation

Inorganic nanoparticles exhibit size-dependent properties that are of interest for applications ranging from biosensing and catalysis to optics and data storage. They are readily available in a wide variety of discrete compositions and sizes. Shape-selective synthesis strategies now also yield shapes other than nanospheres, such as anisotropic metal nanostructures with interesting optical properties. Here we demonstrate that the previously described photoinduced method for converting silver nanospheres into triangular silver nanocrystals—so-called nanoprisms—can be extended to synthesize relatively monodisperse nanoprisms with desired edge lengths in the 30–120 nm range. The particle growth process is controlled using dual-beam illumination of the nanoparticles, and appears to be driven by surface plasmon excitations. We find that, depending on the illumination wavelengths chosen, the plasmon excitations lead either to fusion of nanoprisms in an edge-selective manner or to the growth of the nanoprisms until they reach their light-controlled final size.

On the Ligand's Role in the Fluorescence of Gold Nanoclusters

The fluorescence of metal nanoparticles (such as gold and silver) has long been an intriguing topic and has drawn considerable research interest. However, the origin of fluorescence still remains unclear. In this work, on the basis of atomically monodisperse, 25-atom gold nanoclusters we present some interesting results on the fluorescence from [Au(25)(SR)(18)](q) (where q is the charge state of the particle), which has shed some light on this issue. Our work explicitly shows that the surface ligands (-SR) play a major role in enhancing the fluorescence of gold nanoparticles. Specifically, the surface ligands can influence the fluorescence in two different ways: (i) charge transfer from the ligands to the metal nanoparticle core (i.e., LMNCT) through the Au-S bonds, and (ii) direct donation of delocalized electrons of electron-rich atoms or groups of the ligands to the metal core. Following these two mechanisms, we have demonstrated strategies to enhance the fluorescence of thiolate ligand-protected gold nanoparticles. This work is hoped to stimulate more experimental and theoretical research on the atomic level design of luminescent metal nanoparticles for promising optoelectronic and other applications.

Total Structure Determination of Thiolate-Protected Au38 Nanoparticles

We report the total structure of Au(38)(SC(2)H(4)Ph)(24) nanoparticles determined by single crystal X-ray crystallography. This nanoparticle is based upon a face-fused Au(23) biicosahedral core, which is further capped by three monomeric Au(SR)(2) staples at the waist of the Au(23) rod and six dimeric staples with three on the top icosahedron and other three on the bottom icosahedron. The six Au(2)(SR)(3) staples are arranged in a staggered configuration, and the Au(38)S(24) framework has a C(3) rotation axis.

Quantum Sized Gold Nanoclusters with Atomic Precision

Gold nanoparticles typically have a metallic core, and the electronic conduction band consists of quasicontinuous energy levels (i.e. spacing δ ≪ k(B)T, where k(B)T is the thermal energy at temperature T (typically room temperature) and k(B) is the Boltzmann constant). Electrons in the conduction band roam throughout the metal core, and light can collectively excite these electrons to give rise to plasmonic responses. This plasmon resonance accounts for the beautiful ruby-red color of colloidal gold first observed by Faraday back in 1857. On the other hand, when gold nanoparticles become extremely small (<2 nm in diameter), significant quantization occurs to the conduction band. These quantum-sized nanoparticles constitute a new class of nanomaterial and have received much attention in recent years. To differentiate quantum-sized nanoparticles from conventional plasmonic gold nanoparticles, researchers often refer to the ultrasmall nanoparticles as nanoclusters. In this Account, we chose several typical sizes of gold nanoclusters, including Au(25)(SR)(18), Au(38)(SR)(24), Au(102)(SR)(44), and Au(144)(SR)(60), to illustrate the novel properties of metal nanoclusters imparted by quantum size effects. In the nanocluster size regime, many of the physical and chemical properties of gold nanoparticles are fundamentally altered. Gold nanoclusters have discrete electronic energy levels as opposed to the continuous band in plasmonic nanoparticles. Quantum-sized nanoparticles also show multiple optical absorption peaks in the optical spectrum versus a single surface plasmon resonance (SPR) peak at 520 nm for spherical gold nanocrystals. Although larger nanocrystals show an fcc structure, nanoclusters often have non-fcc atomic packing structures. Nanoclusters also have unique fluorescent, chiral, and magnetic properties. Due to the strong quantum confinement effect, adding or removing one gold atom significantly changes the structure and the electronic and optical properties of the nanocluster. Therefore, precise atomic control of nanoclusters is critically important: the nanometer precision typical of conventional nanoparticles is not sufficient. Atomically precise nanoclusters are represented by molecular formulas (e.g. Au(n)(SR)(m) for thiolate-protected ones, where n and m denote the respective number of gold atoms and ligands). Recently, major advances in the synthesis and structural characterization of molecular purity gold nanoclusters have made in-depth investigations of the size evolution of metal nanoclusters possible. Metal nanoclusters lie in the intermediate regime between localized atomic states and delocalized band structure in terms of electronic properties. We anticipate that future research on quantum-sized nanoclusters will stimulate broad scientific and technological interests in this special type of metal nanomaterial.

Atomically precise gold nanoclusters as new model catalysts.

Many industrial catalysts involve nanoscale metal particles (typically 1-100 nm), and understanding their behavior at the molecular level is a major goal in heterogeneous catalyst research. However, conventional nanocatalysts have a nonuniform particle size distribution, while catalytic activity of nanoparticles is size dependent. This makes it difficult to relate the observed catalytic performance, which represents the average of all particle sizes, to the structure and intrinsic properties of individual catalyst particles. To overcome this obstacle, catalysts with well-defined particle size are highly desirable. In recent years, researchers have made remarkable advances in solution-phase synthesis of atomically precise nanoclusters, notably thiolate-protected gold nanoclusters. Such nanoclusters are composed of a precise number of metal atoms (n) and of ligands (m), denoted as Aun(SR)m, with n ranging up to a few hundred atoms (equivalent size up to 2-3 nm). These protected nanoclusters are well-defined to the atomic level (i.e., to the point of molecular purity), rather than defined based on size as in conventional nanoparticle synthesis. The Aun(SR)m nanoclusters are particularly robust under ambient or thermal conditions (<200 °C). In this Account, we introduce Aun(SR)m nanoclusters as a new, promising class of model catalyst. Research on the catalytic application of Aun(SR)m nanoclusters is still in its infancy, but we use Au₂₅(SR)₁₈ as an example to illustrate the promising catalytic properties of Aun(SR)m nanoclusters. Compared with conventional metallic nanoparticle catalysts, Aun(SR)m nanoclusters possess several distinct features. First of all, while gold nanoparticles typically adopt a face-centered cubic (fcc) structure, Aun(SR)m nanoclusters (<2 nm) tend to adopt different atom-packing structures; for example, Au₂₅(SR)₁₈ (1 nm metal core, Au atomic center to center distance) has an icosahedral structure. Secondly, their ultrasmall size induces strong electron energy quantization, as opposed to the continuous conduction band in metallic gold nanoparticles or bulk gold. Thus, nanoclusters become semiconductors and possess a sizable bandgap (e.g., ~1.3 eV for Au₂₅(SR)₁₈). In addition, Aun(SR)m can be doped with a single atom of other metals, which is of great interest for catalysis, because the catalytic properties of nanoclusters can be truly tuned on an atom-by-atom basis. Overall, atomically precise Aun(SR)m nanoclusters are expected to become a promising class of model catalysts. These well-defined nanoclusters will provide new opportunities for achieving fundamental understanding of metal nanocatalysis, such as insight into size dependence and deep understanding of molecular activation, active centers, and catalytic mechanisms through correlation of behavior with the structures of nanoclusters. Future research on atomically precise nanocluster catalysts will contribute to the fundamental understanding of catalysis and to the new design of highly selective catalysts for specific chemical processes.

Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities

Colloidal nanoparticles are being intensely pursued in current nanoscience research. Nanochemists are often frustrated by the well-known fact that no two nanoparticles are the same, which precludes the deep understanding of many fundamental properties of colloidal nanoparticles in which the total structures (core plus surface) must be known. Therefore, controlling nanoparticles with atomic precision and solving their total structures have long been major dreams for nanochemists. Recently, these goals are partially fulfilled in the case of gold nanoparticles, at least in the ultrasmall size regime (1-3 nm in diameter, often called nanoclusters). This review summarizes the major progress in the field, including the principles that permit atomically precise synthesis, new types of atomic structures, and unique physical and chemical properties of atomically precise nanoparticles, as well as exciting opportunities for nanochemists to understand very fundamental science of colloidal nanoparticles (such as the stability, metal-ligand interfacial bonding, ligand assembly on particle surfaces, aesthetic structural patterns, periodicities, and emergence of the metallic state) and to develop a range of potential applications such as in catalysis, biomedicine, sensing, imaging, optics, and energy conversion. Although most of the research activity currently focuses on thiolate-protected gold nanoclusters, important progress has also been achieved in other ligand-protected gold, silver, and bimetal (or alloy) nanoclusters. All of these types of unique nanoparticles will bring unprecedented opportunities, not only in understanding the fundamental questions of nanoparticles but also in opening up new horizons for scientific studies of nanoparticles.

Kinetically controlled, high-yield synthesis of Au25 clusters.

A facile, low-temperature method has been developed for synthesizing Au25 clusters in high yield. It was discovered that by controlling the formation kinetics of the Au(I) intermediate species, exclusive formation of one-sized clusters (Au25) can be achieved, which represents an important advance in the synthesis of monodisperse gold clusters.

Total Structure and Electronic Properties of the Gold Nanocrystal Au36(SR)24

A golden opportunity: the total structure of a Au(36)(SR)(24) nanocluster reveals an unexpected face-centered-cubic tetrahedral Au(28) kernel (magenta). The protecting layer exhibits an intriguing combination of binding modes, consisting of four regular arch-like staples and the unprecedented appearance of twelve bridging thiolates (yellow). This unique protecting network and superatom electronic shell structure confer extreme stability and robustness.

Phase Transformation Synthesis of Novel Ag2O/Ag2CO3 Heterostructures with High Visible Light Efficiency in Photocatalytic Degradation of Pollutants

Coreshell-like Ag2 O/Ag2 CO3 nanoheterostructures with tailored interface are fabricated by a facile, low-cost and one-step phase transformation method. The unique bandgap structure of the Ag2 O/Ag2 CO3 exhibits high separation efficiency of photogenerated electrons and holes, which effectively protects the Ag2 CO3 semiconductor to avoid its photoreduction and gives rise to high activity and stability in degradation of the typical water pollutants.

Size-Focusing Synthesis, Optical and Electrochemical Properties of Monodisperse Au38(SC2H4Ph)24 Nanoclusters

We report a facile, high yielding synthetic method for preparing truly monodisperse Au(38)(SC(2)H(4)Ph)(24) nanoclusters. The synthetic approach involves two main steps: first, glutathionate (-SG) protected polydisperse Au(n) clusters (n ranging from 38 to approximately 102) are synthesized by reducing Au(I)-SG in acetone; subsequently, the size-mixed Au(n) clusters react with excess phenylethylthiol (PhC(2)H(4)SH) for approximately 40 h at 80 degrees C, which leads to Au(38)(SC(2)H(4)Ph)(24) clusters of molecular purity. Detailed studies by mass spectrometry and UV-vis spectroscopy explicitly show a gradual size-focusing process occurred in the thermal etching-induced growth process. The formula and molecular purity of Au(38)(SC(2)H(4)Ph)(24) clusters are confirmed by electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) mass spectrometry, and size-exclusion chromatography. The optical and electrochemical properties of Au(38)(SC(2)H(4)Ph)(24) clusters show molecule-like behavior and the HOMO-LUMO gap of the cluster was determined to be approximately 0.9 eV. The size focusing growth process is particularly interesting and may be exploited to synthesize other robust gold thiolate clusters.