Dingsheng Wang

Bimetallic Nanocrystals: Liquid-Phase Synthesis and Catalytic Applications

Bimetallic nanocrystals (NCs) with core/shell, heterostructure, or inter-metallic and alloyed structures are emerging as more important materials than monometallic NCs. They are expected to display not only a combination of the properties associated with two distinct metals, but also new properties and capabilities due to a synergy between the two metals. More importantly, bimetallic NCs usually show composition-dependent surface structure and atomic segregation behavior, and therefore more interesting applied potentials in various fields including electronics, engineering, and catalysis. Compared with monometallic NCs, preparation of bimetallic NCs is much more complicated and difficult to be achieved. In recent years, researchers from many groups have made great efforts in this area. This review highlights the recent progress in the chemical synthesis of bimetallic NCs. The control over morphology, size, composition, and structure of bimetallic NCs as well as the exploration of their properties and applications are discussed.

Syntheses of Water-Soluble Octahedral, Truncated Octahedral, and Cubic Pt–Ni Nanocrystals and Their Structure–Activity Study in Model Hydrogenation Reactions

We developed a facile strategy to synthesize a series of water-soluble Pt, Pt(x)Ni(1-x) (0 < x < 1), and Ni nanocrystals. The octahedral, truncated octahedral, and cubic shapes were uniformly controlled by varying crystal growth inhibition agents such as benzoic acid, aniline, and carbon monoxide. The compositions of the Pt(x)Ni(1-x) nanocrystals were effectively controlled by choice of ratios between the Pt and Ni precursors. In a preliminary study to probe their structure-activity dependence, we found that the shapes, compositions, and capping agents strongly influence the catalyst performances in three model heterogeneous hydrogenation reactions.

One-Pot Protocol for Au-Based Hybrid Magnetic Nanostructures via a Noble-Metal-Induced Reduction Process

An effective noble-metal-induced reduction (NMIR) strategy for the synthesis of Au-based hybrid magnetic nanostructures, including Au-Co core-shell nanocrystals and Au-Ni spindly nanostructures, has been developed. This NMIR process provides new insights into the reduction of metal ions in organic solvents and also applies to the synthesis of various bimetallic nanocrystals.

Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction

The development of low-cost, efficient, and stable electrocatalysts for the oxygen reduction reaction (ORR) is desirable but remains a great challenge. Herein, we made a highly reactive and stable isolated single-atom Fe/N-doped porous carbon (ISA Fe/CN) catalyst with Fe loading up to 2.16 wt %. The catalyst showed excellent ORR performance with a half-wave potential (E1/2 ) of 0.900 V, which outperformed commercial Pt/C and most non-precious-metal catalysts reported to date. Besides exceptionally high kinetic current density (Jk ) of 37.83 mV cm-2 at 0.85 V, it also had a good methanol tolerance and outstanding stability. Experiments demonstrated that maintaining the Fe as isolated atoms and incorporating nitrogen was essential to deliver the high performance. First principle calculations further attributed the high reactivity to the high efficiency of the single Fe atoms in transporting electrons to the adsorbed OH species.

Sophisticated Construction of Au Islands on Pt–Ni: An Ideal Trimetallic Nanoframe Catalyst

We have developed a priority-related chemical etching method to transfer the starting Pt-Ni polyhedron to a nanoframe. Utilizing the lower electronegativity of Ni in comparison to Au atoms, in conjunction with the galvanic replacement of catalytically active Au to Ni tops, a unique Au island on a Pt-Ni trimetallic nanoframe is achieved. The design strategy is based on the structural priority mechanism of multimetallic nanocrystals during the synthesis and thus can be generalized to other analogous metal-bimetallic nanocrystal combinations (such as Pd and Cu islands on Pt-Ni nanoframes), which is expected to pave the way for the future development of efficient catalysts.

Single-crystalline octahedral Au-Ag nanoframes.

We report the formation of single-crystalline octahedral Au-Ag nanoframes by a modified galvanic replacement reaction. Upon sequential addition of AgNO(3), CuCl, and HAuCl(4) to octadecylamine solution, truncated polyhedral silver nanoparticles formed first and then changed into octahedral Au-Ag nanoframes, without requiring a conventional Ag removal step with additional oxidation etchant. The nanoframes have 12 sides, and all of the eight {111} faces are empty. The side grows along the [110] direction, and the diameter is less than 10 nm. The selective gold deposition on the high-energy (110) surface, the diffusion, and the selective redeposition of Au and Ag atoms are the key reasons for the formation of octahedral nanoframes.

A Strategy for Designing a Concave Pt–Ni Alloy through Controllable Chemical Etching

This corrosion: Octahedral Pt-Ni alloy nanoparticles (NPs) are converted into concave Pt(3)Ni NPs by a coordination-assisted chemical-etching process. The corroded concave Pt-Ni NPs have a higher density of low-coordinate atoms in steps sites, a decisive property in heterogeneous catalysis.

Highly branched Pt–Ni nanocrystals enclosed by stepped surface for methanol oxidation

Integrated design of nanocatalysts with a preferential surface atomic arrangement, composition, and overall morphology will provide great opportunities to enhance their catalytic activity and durability. In this work, Pt–Ni bimetallic nanobundles (NBs) with branched morphology and stepped surfaces have been prepared by a seed-based diffusion method. For methanol oxidation, the Pt–Ni NBs possess 3.6-fold the activity of conventional Pt nanoparticles (NPs), likely due to the high-density surface atomic steps and the presence of surface Ni species. With the aggregation resistant starlike morphology, the Pt–Ni NBs pertain 55% of initial peak current density after 4000 cycles, while conventional Pt NPs maintain only 10% of that.

NiO nanorings and their unexpected catalytic property for CO oxidation

Nickel oxide (NiO) nanorings were synthesized by controllable thermal decomposition of precursor Ni(OH)(2) nanoplates obtained via the reaction between Ni(NO(3))·6H(2)O and NaOH under hydrothermal conditions. The process of their formation was investigated and an unexpected catalytic property of this novel-shaped material is reported for CO oxidation.

General preparation for Pt-based alloy nanoporous nanoparticles as potential nanocatalysts

Although Raney nickel made by dealloying has been used as a heterogeneous catalyst in a variety of organic syntheses for more than 80 years, only recently scientists have begun to realize that dealloying can generate nanoporous alloys with extraordinary structural characteristics. Herein, we achieved successful synthesis of a variety of monodisperse alloy nanoporous nanoparticles via a facile chemical dealloying process using nanocrystalline alloys as precursors. The as-prepared alloy nanoporous nanoparticles with large surface area and small pores show superior catalytic properties compared with alloyed nanoparticles. It is believed that these novel alloy nanoporous nanoparticles would open up new opportunities for catalytic applications.