Metal-Semiconductor Heteronanocrystals with Desired Configurations for Plasmonic Photocatalysis.

Precise control over the topology of plasmonic metal-semiconductor heteronanostructures is essential for fully harnessing their plasmonic function and hence for designing innovative solar energy conversion platforms. Here, we present a rational synthesis strategy for the realization of plasmonic metal-semiconductor heteronanocrystals with intended configurations through the site-selective overgrowth of semiconductor Cu2O on desired sites of anisotropic Au nanocrystals. Both the exploitation of structural characteristics of Au nanocrystals and the selective stabilization of their surfaces are keys to the construction of heteronanocrystals with a specific configuration. Our approach can provide an opportunity to precisely explore the link between the solar energy conversion efficiency and the structure of heteronanocrystals as well as to obtain important insights into the underpinning mechanism. Heteronanocrystals produced by Cu2O overgrowth preferentially on the multiple high-curvature sites of Au nanocrystals exhibited prominent photocatalytic hydrogen production activity due to efficient charge separation by strong plasmon excitation at the Au-Cu2O interface and subsequent sustainable hot electron transfer from Au to Cu2O.

Ultrathin Free-Standing Ternary-Alloy Nanosheets.

A synthesis strategy for the preparation of ultrathin free-standing ternary-alloy nanosheets is reported. Ultrathin Pd-Pt-Ag nanosheets with a thickness of approximately 3 nm were successfully prepared by co-reduction of the metal precursors in an appropriate molar ratio in the presence of CO. Both the presence of CO and the interplay between the constituent metals provide fine control over the anisotropic two-dimensional growth of the ternary-alloy nanostructure. The prepared Pd-Pt-Ag nanosheets were superior catalysts of ethanol electrooxidation owing to their specific structural and compositional characteristics. This approach will pave the way for the design of multicomponent 2D nanomaterials with unprecedented functions.

Universal sulfide-assisted synthesis of M-Ag heterodimers (M = Pd, Au, Pt) as efficient platforms for fabricating metal-semiconductor heteronanostructures.

We report a universal sulfide-assisted synthesis strategy to prepare dumbbell-like M-Ag heterodimers (M = Pd, Au, Pt). Sulfide ions can give fine control over the reaction kinetics of Ag precursors, resulting in the anisotropic overgrowth of Ag to realize the dumbbell-like heterodimers irrespective of the surface facets or components of the M domain. The M-Ag heterodimers were facilely transformed to M-Ag2S heterodimers via a simple sulfidation reaction. This study provides a versatile approach to realizing not only metal-metal heterodimers but also semiconductor-metal heterodimers and will pave the way for designing heteronanostructures with unprecedented morphologies and functions.

Compositional dependence of Co- and Mo-supported beta zeolite for selective one-step hydrotreatment of methyl palmitate to produce bio jet fuel range hydrocarbons.

For producing a drop-in bio jet fuel, one-step hydrotreatment, which includes deoxygenation, isomerization and cracking in one step, is essential to overcome the typical biofuel drawbacks due to high oxygen content, out of jet fuel range hydrocarbons, and low isomerization degree. Herein, Co- or/and Mo-supported Beta(25) zeolites with various Co/Mo ratios were prepared as transition metal-supported zeolite catalysts without the need for sulfidation of conventional transition metal catalysts. Based on the catalyst characterization, the Co/Mo ratio alters the metal phase with the appearance of CoMoO4 and the altered Co metal phase strongly influences the acidic properties of Beta(25) by the formation of Lewis (L) acid sites with different strengths as Co3O4 and CoMoO4 for strong and weak L acid sites, respectively. The catalytic activities were investigated for hydrotreatment of methyl palmitate as a biofuel model compound of fatty acid methyl esters. Primarily, Co is required for deoxygenation and Mo suppresses overcracking to enhance the yield of jet fuel range hydrocarbons. The Co/Mo ratio plays an important role to improve the C8-C16 selectivity by modifying the acidic properties to inhibit excessive cracking. Co5Mo10/Beta(25) achieved the best catalytic performance with the conversion of 94.2%, C8-C16 selectivity of 89.7 wt%, and high isomer ratio of 83.8% in organic liquid product. This unique modification of acidic properties will find use in the design of optimal transition metal-supported zeolite catalysts for selective one-step hydrotreatment to produce bio jet fuel range hydrocarbons.

Hexoctahedral Au nanocrystals with high-index facets and their optical and surface-enhanced Raman scattering properties.

Au nanocrystals (NCs) with an unprecedented hexoctahedral structure enclosed exclusively by high-index {321} facets have been prepared for the first time. Manipulating the NC growth kinetics by controlling the amount of reductant and the reaction temperature in the presence of a suitable surfactant was the key synthetic lever for controlling the morphology of the Au NCs. The hexoctahedral Au NCs exhibited efficient optical and surface-enhanced Raman scattering activities due to their unique morphological characteristics.

Synthesis of Pd-Pt Ultrathin Assembled Nanosheets as Highly Efficient Electrocatalysts for Ethanol Oxidation.

Control over composition and morphology of nanocrystals (NCs) is significant to develop advanced catalysts applicable to polymer electrolyte membrane fuel cells and further overcome the performance limitations. Here, we present a facile synthesis of Pd-Pt alloy ultrathin assembled nanosheets (UANs) by regulating the growth behavior of Pd-Pt nanostructures. Iodide ions supplied from KI play as capping agents for the {111} plane to promote 2-dimensional (2D) growth of Pd and Pt, and the optimal concentrations of cetyltrimethylammonium chloride and ascorbic acid result in the generation of Pd-Pt alloy UANs in high yield. The prepared Pd-Pt alloy UANs exhibited the remarkable enhancement of the catalytic activity and stability toward ethanol oxidation reaction compared to irregular-shaped Pd-Pt alloy NCs, commercial Pd/C, and commercial Pt/C. Our results confirm that the Pd-Pt alloy composition and ultrathin 2D morphology offer high accessible active sites and favorable electronic structure for enhancing electrocatalytic activity.

The controlled synthesis of plasmonic nanoparticle clusters as efficient surface-enhanced Raman scattering platforms.

A facile aqueous synthesis method for the preparation of Au nanoparticle clusters by the controlled galvanic replacement of Ag nanoparticles with Au precursors is described. The prepared clusters showed both significantly enhanced surface-enhanced Raman scattering activity and stability.

Nitrogen-Doped Pt/C Electrocatalysts with Enhanced Activity and Stability toward the Oxygen Reduction Reaction.

Recently, nitrogen-doped carbon materials have proved to be effective catalytic platforms for the oxygen reduction reaction (ORR). Despite the recent synthetic advances for the preparation of nitrogen-incorporated carbon materials, the low-temperature and water-based synthesis of nitrogen-doped carbon materials has rarely been explored due to the difficulties in nitrogen-doping under such mild conditions. Here, nitrogen-doped Pt/C (Pt/NC) catalysts are prepared using a facile, low-temperature, aqueous-phase method. Hydrazine treatment of a Pt/C catalyst successfully yields Pt/NC with controlled nitrogen content. The as-prepared Pt/NC catalysts exhibit enhanced electrocatalytic activity and stability toward ORR in comparison to nitrogen-free Pt/C, and their ORR activities are highly dependent on the level of nitrogen-doping. The Pt/NC catalyst containing 2.0 at % nitrogen results in the largest improvement of ORR activity.

Composition-controlled PtCo alloy nanocubes with tuned electrocatalytic activity for oxygen reduction.

Modification of the electronic structure and lattice contraction of Pt alloy nanocatalysts through control over their morphology and composition has been a crucial issue for improving their electrocatalytic oxygen reduction reaction (ORR) activity. In the present work, we synthesized PtCo alloy nanocubes with controlled compositions (Pt(x)Co NCs, x = 2, 3, 5, 7, and 9) by regulating the ratio of surfactants and the amount of Co precursor to elucidate the effect of the composition of nanocatalysts on their ORR activity. Pt(x)Co NCs had a Pt-skin structure after electrochemical treatment. The electrocatalysis experiments revealed a strong correlation between ORR activity and Co composition. Pt3Co NCs exhibited the best ORR performance among the various Pt(x)Co NCs. From density functional theory calculations, a typical volcano-type relationship was established between ORR activity and oxygen binding energy (E(OB)) on NC surfaces, which showed that Pt3Co NCs had the optimal E(OB) to achieve the maximum ORR activity. X-ray photoelectron spectroscopy and X-ray diffraction measurements demonstrated that the electronic structure and lattice contraction of the Pt(x)Co NCs could be tuned by controlling the composition of NCs, which are highly correlated with the trends of E(OB) change.

One-pot synthesis of monodisperse 5 nm Pd-Ni nanoalloys for electrocatalytic ethanol oxidation.

Highly monodisperse 5 nm Pd-Ni alloy nanoparticles (NPs) were prepared by the reduction of Pd(acac)(2)/Ni(acac)(2) mixtures with tert-butylamine-borane complex (TBAB) in the presence of oleic acid (OA) and oleylamine (OAm). Employing TBAB as an effective reductant and OA/OAm combination as an effective stabilizing agent is crucial to the formation of monodisperse Pd-Ni NPs. Experimental results collectively verify that the Pd-Ni alloy NPs form through the sequential nucleation-interdiffusion process and the simultaneous reduction of both metal precursors by the one-pot protocol is the key to the formation of homogeneous NPs. The Pd-Ni NPs were well-dispersed on carbon supports and chemically dealloyed after acetic acid washing through the selective dissolution of the less noble Ni component. The Pd-Ni NP catalysts exhibited much higher electrocatalytic activity and stability for ethanol oxidation than those of a commercial Pd/C catalyst.