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.

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

http://pubs.acs.org/doi/pdfplus/10.1021/cr300162p

Deep Eutectic Solvents (DESs) and Their Applications

[Yang, Hua Gui; Sun, Cheng Hua; Qiao, Shi Zhang; Liu, Gang; Smith, Sean Campbell; Lu, Gao Qing] Univ Queensland, ARC Ctr Excellence Funct Nanomat, Sch Engn, Brisbane, Qld 4072, Australia. [Yang, Hua Gui; Sun, Cheng Hua; Qiao, Shi Zhang; Liu, Gang; Smith, Sean Campbell; Lu, Gao Qing] Univ Queensland, Australian Inst Bioengn & Nanotechnol, Ctr Computat Mol Sci, Brisbane, Qld 4072, Australia. [Zou, Jin] Univ Queensland, Ctr Microscopy & Microanal, Brisbane, Qld 4072, Australia. [Zou, Jin] Univ Queensland, Sch Engn, Brisbane, Qld 4072, Australia. [Liu, Gang; Cheng, Hui Ming] Chinese Acad Sci, Met Res Inst, Shenyang Natl Lab Mat sci, Shenyang 110016, Peoples R China.;Lu, GQ (reprint author), Univ Queensland, ARC Ctr Excellence Funct Nanomat, Sch Engn, Brisbane, Qld 4072, Australia;s.qiao@uq.edu.au maxlu@uq.edu.au

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Anatase TiO(2) single crystals with a large percentage of reactive facets

The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core–shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided.

http://repository.ust.hk/ir/bitstream/1783.1-77094/1/acs.chemrev.5b00462_withlink.pdf

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction

Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal–support interaction, and metal–reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results o...

Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

Ru nanoparticles supported on partially reduced TiO2 as highly efficient catalyst for hydrogen evolution

This paper reports an overpotential-dependent shape evolution of gold nanocrystals (Au NCs) in a choline chloride-urea (ChCl-urea) based deep eutectic solvent (DES). It was found that the growth overpotentials play a key role in tuning the shape of Au NCs. The shape evolution of Au NCs successively from concave rhombic dodecahedra (RD) to concave cubes, octopods, cuboctahedral boxes, and finally, to hollow octahedra (OH) was achieved by carefully controlling the growth overpotentials in the range from –0.50 to –0.95 V (vs. Pt quasi-reference electrode). In addition, the presence of urea was important in the shape evolution of Au NCs. The surface structure of the as-prepared Au NCs was comprehensively characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical studies. It was demonstrated that the electrocatalytic activity of the as-prepared Au NCs for D-glucose electrooxidation was sensitively dependent on their morphologies. The results illustrated that the dehydrogenated glucose adsorbed on concave RD and concave cubic Au NCs was preferentially transformed to gluconolactone at low electrode potentials. Subsequent gluconolactone oxidation occurred favorably on octopods with {111}-truncated arms and hollow OH at high electrode potential. This study opens up a new approach to develop the surface-structurecontrolled growth of Au NCs by combining DES with electrochemical techniques. In addition, it is significant for the tuning of the electrocatalytic properties of NCs.

Overpotential-dependent shape evolution of gold nanocrystals grown in a deep eutectic solvent

Intermetallic PtBi Nanoplates with High Catalytic Activity towards Electro-oxidation of Formic Acid and Glycerol

Because high-index facets (HIFs) possess high surface energy, the metal nanoparticles enclosed with HIFs are eliminated during their growth in a conventional shape-controlled synthesis due to the thermodynamics that drives the particles minimizing their total surface energy. This study develops a double-step potential method to prepare an unprecedentedly stellated Au nanocrystals (NCs) bounded by high-index {711} and {331} facets in deep eutectic solvent (DES) medium. The formation of Au NCs bounded by HIFs was systematically studied. It has demonstrated that the shapes of Au NCs are strongly dependent on the size of seeds and the growth potentials as well as the urea adsorbates in the DES. By adjusting the size of seeds and the growth potentials, the stellated Au NCs can be transformed into concave hexoctahedra (HOH) with high-index {421} facets and concave trisoctahedra (TOH) with high-index {991} facets. The electrocatalytic activities of the as-prepared Au NCs are evaluated by glucose oxidation. Thank...

Seeds and Potentials Mediated Synthesis of High-Index Faceted Gold Nanocrystals with Enhanced Electrocatalytic Activities

Pyrolyzed Fe/N/C catalyst has been considered as the most promising candidate to replace Pt for oxygen reduction reaction (ORR) in fuel cells. However, poor stability of Fe/N/C catalyst, mainly attributed to the oxidation corrosion by aggressive •OH radical, severely hampers its applications. However, the exact mechanism for generation of •OH is unclear yet. Herein, we developed a fluorescent method to effectively detect •OH generated from ORR on Fe/N/C catalyst by using coumarin as a fluorescent probe. A great difference in potential dependence between •OH and H2O2 generated from the ORR was observed, which suggests that •OH is not generated from the decomposition of H2O2 as traditional viewpoint.

Na Tian

Papers

Ru nanoparticles supported on partially reduced TiO2 as highly efficient catalyst for hydrogen evolution

Overpotential-dependent shape evolution of gold nanocrystals grown in a deep eutectic solvent

Intermetallic PtBi Nanoplates with High Catalytic Activity towards Electro-oxidation of Formic Acid and Glycerol

Seeds and Potentials Mediated Synthesis of High-Index Faceted Gold Nanocrystals with Enhanced Electrocatalytic Activities

Fluorescence detection of hydroxyl radical generated from oxygen reduction on Fe/N/C catalyst