Synthesis of Pd Nanocrystals Enclosed by {100} Facets and with Sizes 〈10 nm for Application in CO Oxidation

The catalytic activity of noble-metal nanocrystals is mainly determined by their sizes and the facets exposed on the surface. For single crystals, it has been demonstrated that the Pd（100） surface is catalytically more active than both Pd（110） and Pd（111） surfaces for the CO oxidation reaction. Here we report the synthesis of Pd nanocrystals enclosed by {100} facets with controllable sizes in the range of 6-18 nm by manipulating the rate of reduction of the precursor. UV-vis spectroscopy studies indicate that the rate of reduction of Na2PdC14 can be controlled by adjusting the concentrations of Br- and C1- ions added to the reaction mixture. Pd nanocrystals with different sizes were immobilized on ZnO nanowires and evaluated as catalysts for CO oxidation. We found that the activity of this catalytic system for CO oxidation showed a strong dependence on the nanocrystal size. When the size of the Pd nanocrystals was reduced from 18 nm to 6 nm, the maximum conversion rate was significantly enhanced by a factor of -10 and the corresponding maximum conversion temperature was lowered by -80℃.

Nucleation and Growth Mechanisms for Pd-Pt Bimetallic Nanodendrites and Their Electrocatalytic Properties

In a seed-mediated synthesis, nanocrystal growth is often described by assuming the absence of homogeneous nucleation in the solution. Here we provide new insights into the nucleation and growth mechanisms underlying the formation of bimetallic nanodendrites that are characterized by a dense array of Pt branches anchored to a Pd nanocrystal core. These nanostructures can be easily prepared by a one-step, seeded growth method that involves the reduction of K2PtCl4 by L-ascorbic acid in the presence of 9-nm truncated octahedral Pd seeds in an aqueous solution. Transmission electron microscopy (TEM) and high-resolution TEM analyses revealed that both homogeneous and heterogeneous nucleation of Pt occurred at the very early stages of the synthesis and the Pt branches grew through oriented attachment of small Pt particles that had been formed via homogeneous nucleation. These new findings contradict the generally accepted mechanism for seeded growth that only involves heterogeneous nucleation and simple growth via atomic addition. We have also investigated the electrocatalytic properties of the Pd-Pt nanodendrites for the oxygen reduction and formic acid oxidation reactions by conducting a comparative study with foam-like Pt nanostructures prepared in the absence of Pd seeds under otherwise identical conditions.

Shape-controlled syntheses of rhodium nanocrystals for the enhancement of their catalytic properties

Rhodium （Rh） is a critical component of many catalysts for a variety of chemical transformation processes. Controlling the shape of Rh nanocrystals offers an effective route to the optimization of their catalytic performance owing to a close correlation between the catalytic activity/selectivity and the surface atomic structure. It also helps to substantially reduce the loading amount and thus achieve a sustainable use of this scarce and precious metal. In this review article, we focus on recent progress in the shape-controlled synthesis of Rh nanocrystals with the goal of enhandng their catalytic properties. Both traditional and newly- developed synthetic strategies and growth mechanisms will be discussed, including those based on the use of surface capping agents, manipulation of reduction kinetics, control of surface diffusion rate, management of oxidation etching, and electrochemical alteration. We also use two examples to highlight the unique opportunities offered by shape-controlled synthesis for enhancing the use of this metal in catalytic applications. The strategies can also be extended to other precious metals in an effort to advance the production of cost-effective catalysts.

New Insights into the Growth Mechanism and Surface Structure of Palladium Nanocrystals

This paper presents a systematic study of the growth mechanism for Pd nanobars synthesized by reducing Na_(2)PdCl_(4) with L-ascorbic acid in an aqueous solution in the presence of bromide ions as a capping agent.Transmission electron microscopy(TEM)and high-resolution TEM analyses revealed that the growth at early stages of the synthesis was dominated by particle coalescence,followed by shape focusing via recrystallization and further growth via atomic addition.We also investigated the detailed surface structure of the nanobars using aberration-corrected scanning TEM and found that the exposed{100}surfaces contained several types of defects such as an adatom island,a vacancy pit,and atomic steps.Upon thermal annealing,the nanobars evolved into a more thermodynamically favored shape with enhanced truncation at the corners.

Synthesis and Optical Properties of Cubic Gold Nanoframes

This paper describes a facile method of preparing cubic Au nanoframes with open structures via the galvanic replacement reaction between Ag nanocubes and AuCl_(2)^(-).A mechanistic study of the reaction revealed that the formation of Au nanoframes relies on the diffusion of both Au and Ag atoms.The effect of the edge length and ridge thickness of the nanoframes on the localized surface plasmon resonance peak was explored by a combination of discrete dipole approximation calculations and single nanoparticle spectroscopy.With their hollow and open structures,the Au nanoframes represent a novel class of substrates for applications including surface plasmonics and surface-enhanced Raman scattering.

Growth and Patterning of Pt Nanowires on Silicon Substrates

This paper describes a simple procedure for growing dense fi lms of Pt nanowires directly on silicon substrates by modifying the surface through chemical or physical means.In the former,a self-assembled monolayer of(3-mercaptopropyl)-trimethoxysilane(MPTMS)is applied which can strongly bind Pt(0)nuclei to the surface through Pt S linkages.Once attached,the Pt(0)nuclei can act as catalytic sites for the growth of Pt nanowires along the〈111〉direction.Alternately,relief features are physically created on the surface in order to generate nucleation and binding sites for Pt(0)nuclei,due to the higher free energy associated with a rough surface.Additionally,Pt nanowires have been successfully produced in well-defined patterns by scouring grooves on the silicon surface or by photochemically patterning the MPTMS monolayers with a shadow mask.We have also measured the electrochemical properties of these immobilized or patterned Pt nanowires.The results provide an effective route to producing dense fi lms of Pt nanowires with high surface areas for various electrochemical applications.

Shape-Controlled Synthesis of Copper Nanocrystals for Plasmonic,Biomedical,and Electrocatalytic Applications

CONSPECTUS:As a metal that can occur in nature in the elemental form,copper(Cu)has been used by humans since ca.8000 BC.With most properties matching those of Ag and Au,Cu has played a more significant role in commercial applications owing to its much higher(the 25th among all elements)abundance in Earth’s crust and thus more affordable price.In addition to its common use as a conductor of heat and electricity,it is a constituent of various metal alloys for hardware,coins,strain gauges,and thermocouples.

Facile synthesis of Pd concave nanocubes： From kinetics to mechanistic understanding and rationally designed protocol

We report a rationally designed one-pot method for the facile synthesis of Pd concave nanocubes in an aqueous solution at room temperature by manipulating the reduction kinetics through the selection of a proper combination of a salt precursor （PdBr4^2-） and reductant （sodium ascorbate）. Our kinetic analysis demonstrates that, through this selection, the nucleation and growth of Pd nanocrystals could be effectively separated into two kinetic regimes involving distinctive reduction pathways： i） solution reduction for the initial formation of single-crystal seeds and ii） surface reduction for the formation of concave nanocrystals via autocatalytic growth from the single-crystal seeds. The suppressed surface diffusion at room temperature, when coupled with the capping effect of bromide ions, ultimately leads to the formation of concave nanocubes with an asymmetric shape and high-index facets, whose synthesis would otherwise require multiple steps and the use of elevated temperatures.

Deterministic Synthesis of Pd Nanocrystals Enclosed by High-Index Facets and Their Enhanced Activity toward Formic Acid Oxidation

Noble-metal nanocrystals enclosed by high-index facets are of growing interest due to their enhanced catalytic performance in a variety of reactions.Herein,we report the deterministic synthesis of Pd nanocrystals encased by high-index facets by controlling the rate of deposition(V_(deposition))relative to that of surface diffusion(V_(diffusion)).For octahedral seeds with truncated corners,a reduction rate(and thus deposition rate)faster than that of surface diffusion(i.e.,V_(deposition)/V_(diffusion)>1)led to the formation of concave trisoctahedra(TOH)with high-index facets.When the reduction was slowed down,in contrast,surface diffusion dominated the growth pathway.In the case of V_(deposition)/V_(diffusion)≈1,truncated octahedra with enlarged sizes were produced.When the reduction rate was between these two extremes,we obtained concave tetrahexahedra(THH)without or with truncation.Similar growth patterns were also observed for the cuboctahedral seeds.When the Pd octahedra,concave TOH,and concave THH were tested for electrocatalyzing the formic acid oxidation(FAO)reaction,those with high-index facets were advantageous over the conventional Pd octahedra enclosed by{111}facets.This work not only contributes to the understanding of surface diffusion and its role in nanocrystal growth but also offers a general protocol for the synthesis of nanocrystals enclosed by high-index facets.