Development of an amphiphilic resin‐dispersion of nanopalladium and nanoplatinum catalysts: Design,preparation, and their use in green organic transformations

An amphiphilic polymer resin‐dispersion of nanoparticles of palladium was designed and prepared with a view toward use for catalysis in water. The amphiphilic polystyrene‐poly(ethylene glycol) (PS‐PEG) resin‐dispersion of nanoparticles of palladium exhibited high catalytic performance in the hydrodechlorination of chloroarenes under aqueous conditions. The amphiphilic resin‐supported nanopalladium and nanoplatinum particles also catalyzed aerobic oxidation of various alcohols including nonactivated aliphatic and alicyclic alcohols, which is one of the most fundamental and important yet immature processes in organic chemistry, in water under an atmospheric pressure of oxygen gas to form aldehydes, ketones, and carboxylic acids to meet green chemical requirements. Viologen polymer‐supported nanopalladium catalyst realized α‐alkylation of ketones with primary alcohols as the alkylating agents. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 51–65; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20165     

Shape‐controlled synthesis of Pt nanocrystals: an evolution of the tetrahedral shape

Platinum nanocrystals with sizes smaller than 10 nm are obtained by H₂‐reduction of aqueous K₂PtCl₆ in the presence of different concentrations of poly (N‐vinyl‐2‐pyrrolidone; PVP:M_w ≈ 360 000) at pH = 2.5–7.0. Tetrahedral Pt nanocrystals (3–10 nm) are produced with high selectivity (73–83% by number) at moderate PVP:K₂PtCl₆ ratios. The co‐existing round/spheroidal crystallites are found to be smaller than the tetrahedrally shaped ones in the systems of varying K₂PtCl₆:PVP ratios. Careful examinations of the particle size and shape evolution of the crystallites at different stages of the crystal growth with transmission electron microscopy (TEM) and ultraviolet–visible absorption spectroscopy (UV–vis) suggest that the tetradedrally shaped Pt crystallites share the same type of nuclei with the round ones at the early stage of the crystal formation. Evolution of the tetrahedral shape happens in the later slow crystal growth. Copyright © 2006 John Wiley & Sons, Ltd.     

Size‐, Shape‐ and Composition‐Dependent Alloying Ability of Bimetallic Nanoparticles

Based on the surface‐area‐difference model, the formation enthalpies and the formation Gibbs free energies of bimetallic nanoparticles are calculated by considering size and shape effects. Composition–critical size diagrams were graphed for bulk immiscible bimetallic nanoparticles with the developed model. The results reveal that both the formation enthalpy and formation Gibbs free energy decrease with the decrease of particle size. The effect of rising temperature is similar to the diminishing of particle size on reducing the formation Gibbs free energy. Contrary to the positive formation enthalpy of the bulk immiscible system, a negative formation enthalpy is obtained when the particles are smaller than a critical size. With the decrease of size, the alloying process first takes place in the dilute solute regions, then broadens to the dense solute regions and finally, particles with all compositions can be alloyed. The composition–critical size diagram is classified into three regions by the critical size curves with shape factors of 1 and 1.49, that is, the non‐alloying region, alloying region and possible alloying region. The model predictions correspond well with experimental evidences and computer simulation results for Cu–Ag, Au–Ni, Ag–Pt and Au–Pt systems.     

Shape‐Controlled Surface‐Coating to Pd@Mesoporous Silica Core–Shell Nanocatalysts with High Catalytic Activity and Stability

Cubic Pd nanocrystals with shape‐controlled mesoporous silica shells have been theoretically designed and successfully synthesized for investigating the effect of a porous nanoshell on catalytic performance of the core. Cubic Pd@cubic mesoporous silica keeps activity of all facets and shows highest catalytic activity and enhanced reusability in the hydrogenation of nitrobenzene.     

Shape‐Controlled Growth of Carbon Nanostructures: Yield and Mechanism

Carbon nanostructures with precisely controlled shapes are difficult materials to synthesize. A facet‐selective‐catalytic process was thus proposed to synthesize polymer‐linked carbon nanostructures with different shapes, covering straight carbon nanofiber, carbon nano Y‐junction, carbon nano‐hexapus, and carbon nano‐octopus. A thermal chemical vapor deposition process was applied to grow these multi‐branched carbon nanostructures at temperatures lower than 350 °C. Cu nanoparticles were utilized as the catalyst and acetylene as the reaction gas. The growth of those multi‐branched nanostructures was realized through the selective growth of polymer‐like sheets on certain indexed facets of Cu catalyst. The vapor–facet–solid (VFS) mechanism, a new growth mode, has been proposed to interpret such a growth in the steps of formation, diffusion, and coupling of carbon‐containing oligomers, as well as their final precipitation to form nanostructures on the selective Cu facets.     

Dependence of CO oxidation on Pt nanoparticle shape: a shape‐selective approach to the synthesis of PEMFC catalysts

In real catalyst systems, it is difficult to establish a correlation between catalytic properties and the shape (crystal planes, corners and steps) of the active catalytic particles. In this paper we present a clear shape dependence of the catalytic properties of a Vulcan‐supported fuel cell catalyst having 4 nm cubo‐octahedral platinum(0) nanocrystallites with (111) and (100) surfaces stabilized by sodium polyacrylate. The electrode materials were characterized by CO‐stripping cyclic voltammetry and transmission electron microscopy (TEM), showing that no agglomeration had occurred among the nanoparticles on the catalyst surfaces. Copyright © 2007 John Wiley & Sons, Ltd.     

Catalysis of hydrosilylation,part XXII: Polymer-protected immobilized platinum complex catalysts for gas-phase hydrosilylation of acetylene

A platinum catalyst (hexachloroplatinic acid dissolved in ethanol) was immobilized by anchoring via amine and mercapto groups to silica followed by formation of a polymer layer which protected the catalyst against leaching. These catalysts (A and B) as well as precatalysts (S_A-Pt, S_B-Pt) which were not protected by polymer were tested in the gas-phase hydrosilylation reaction of acetylene with trichlorosilane. The catalytic parameters (yield 80%, selectivity 100%) obtained under optimal conditions prove the advantage of catalyst A over 300 h reaction time by the flow method.     

Why platinum catalysts involving ligands with large bite angle are so efficient in the allylation of amines: design of a highly active catalyst and comprehensive experimental and DFT study

The platinum-catalyzed allylation of amines with allyl alcohols was studied experimentally and theoretically. The complexes [Pt(eta(3)-allyl)(dppe)]OTf (2) and [Pt(eta(3)-allyl)(DPP-Xantphos)]PF(6) (5) were synthesized and structurally characterized, and their reactivity toward amines was explored. The bicyclic aminopropyl complex [Pt(CH(2)CH(2)CH(2)NHBn-kappa-C,N)(dppe)]OTf (3) was obtained from the reaction of complex 2 with an excess of benzylamine, and this complex was shown to be a deactivated form of catalyst 2. On the other hand, reaction of complex 5 with benzylamine and allyl alcohol led to formation of the 16-VE platinum(0) complex [Pt(eta(2)-C(3)H(5)OH)(DPP-Xantphos)] (7), which was structurally characterized and appears to be a catalytic intermediate. A DFT study showed that the mechanism of the platinum-catalyzed allylation of amines with allyl alcohols differs from the palladium-catalyzed process, since it involves an associative ligand-exchange step involving formation of a tetracoordinate 18-VE complex. This DFT study also revealed that ligands with large bite angles disfavor the formation of platinum hydride complexes and therefore the formation of a bicyclic aminopropyl complex, which is a thermodynamic sink. Finally, a combination of 5 and a proton source was shown to efficiently catalyze the allylation of a broad variety of amines with allyl alcohols under mild conditions.     

One‐pot dual size‐ and shape selective synthesis of tetrahedral Pt nanoparticles

One‐pot dual size‐ and shape‐selective synthesis of tetrahedral Pt nanoparticles is achieved using the pre‐prepared Pt nanoparticles as the ‘external seeds’, and controlling the slow diffusional growth under hydrogen reduction in the presence of PVP as the capping agent. Copyright © 2006 John Wiley & Sons, Ltd.     

Towards the design of novel boron‐ and nitrogen‐substituted ammonia‐borane and bifunctional arene ruthenium catalysts for hydrogen storage

Electronic‐structure density functional theory calculations have been performed to construct the potential energy surface for H₂ release from ammonia‐borane, with a novel bifunctional cationic ruthenium catalyst based on the sterically bulky β‐diketiminato ligand (Schreiber et al., ACS Catal. 2012, 2, 2505). The focus is on identifying both a suitable substitution pattern for ammonia‐borane optimized for chemical hydrogen storage and allowing for low‐energy dehydrogenation. The interaction of ammonia‐borane, and related substituted ammonia‐boranes, with a bifunctional η⁶‐arene ruthenium catalyst and associated variants is investigated for dehydrogenation. Interestingly, in a number of cases, hydride‐proton transfer from the substituted ammonia‐borane to the catalyst undergoes a barrier‐less process in the gas phase, with rapid formation of hydrogenated catalyst in the gas phase. Amongst the catalysts considered, N,N‐difluoro ammonia‐borane and N‐phenyl ammonia‐borane systems resulted in negative activation energy barriers. However, these types of ammonia‐boranes are inherently thermodynamically unstable and undergo barrierless decay in the gas phase. Apart from N,N‐difluoro ammonia‐borane, the interaction between different types of catalyst and ammonia borane was modeled in the solvent phase, revealing free‐energy barriers slightly higher than those in the gas phase. Amongst the various potential candidate Ru‐complexes screened, few are found to differ in terms of efficiency for the dehydrogenation (rate‐limiting) step. To model dehydrogenation more accurately, a selection of explicit protic solvent molecules was considered, with the goal of lowering energy barriers for H‐H recombination. It was found that primary (1°), 2°, and 3° alcohols are the most suitable to enhance reaction rate. © 2014 Wiley Periodicals, Inc.     

Controlled Synthesis of Water‐Dispersible Faceted Crystalline Copper Nanoparticles and Their Catalytic Properties

We report a solution‐phase synthetic route to copper nanoparticles with controllable size and shape. The synthesis of the nanoparticles is achieved by the reduction of copper(II) salt in aqueous solution with hydrazine under air atmosphere in the presence of poly(acrylic acid) (PAA) as capping agent. The results suggest that the pH plays a key role for the formation of pure copper nanoparticles, whereas the concentration of PAA is important for controlling the size and geometric shape of the nanoparticles. The average size of the copper nanoparticles can be varied from 30 to 80 nm, depending on the concentration of PAA. With a moderate amount of PAA, faceted crystalline copper nanoparticles are obtained. The as‐synthesized copper nanoparticles appear red in color and are stable for weeks, as confirmed by UV/Vis and X‐ray photoemission (XPS) spectroscopy. The faceted crystalline copper nanoparticles serve as an effective catalyst for N‐arylation of heterocycles, such as the C? N coupling reaction between p‐nitrobenzyl chloride and morpholine producing 4‐(4‐nitrophenyl)morpholine in an excellent yield under mild reaction conditions. Furthermore, the nanoparticles are proven to be versatile as they also effectively catalyze the three‐component, one‐pot Mannich reaction between p‐substituted benzaldehyde, aniline, and acetophenone affording a 100 % conversion of the limiting reactant (aniline).     

Graphene‐mesoporous anatase TiO2 nanocomposite: A highly efficient and recyclable heterogeneous catalyst for one‐pot multicomponent synthesis of benzodiazepine derivatives

The potential to bias chemical reaction pathways is a significant goal for physicists and material researchers to design revolutionary materials. Recently, two‐dimensional materials have appeared as a promising candidate for exploring novel catalyst activity in organic reaction. In this context, herein we report an easy and efficient synthesis of substituted benzodiazepines in high yields through the graphene‐based mesoporous TiO₂ nanocomposite (Gr@TiO₂ NCs) catalyst. To validate the merits of the Gr@TiO₂ NCs as a catalyst, we have also designed TiO₂ nanoparticle (NPs) under similar conditions. Successful comprehension realization of Gr@TiO₂ NCs and TiO₂ NPs were concluded from the XRD, SEM, HR‐TEM, EDS elemental mapping, FT‐IR, Raman, UV–Vis and TGA analysis. Gr@TiO₂ NCs has the propitious catalyst performance (~98%) over the TiO₂ NPs (~77%), which could be scrutinized in terms of graphene support toward the TiO₂ NPs and enable the large contact area between graphene and TiO₂ NPs. Incorporated graphene maintaining TiO₂ as a catalytically active and attracting electron to site isolation, as well as protecting TiO₂ from oxidative degradation during the reaction. Moreover, the role of graphene is suggested to prolonged reaction duration, yield and unaltered throughout the reaction because of the π‐π interaction between graphene and TiO₂ NPs. Additionally, the catalyst is recycled by filtration and reprocessed six times without having a significant loss in its catalytic activity.     

Self‐assembling directed synthesis of a novel terephthalamide‐bridged ladderlike polysiloxane

A novel, soluble terephthalamide‐bridged ladderlike polysiloxane ( L ) was synthesized successfully for the first time by stepwise coupling polymerization. The process involved the hydrogen‐bonding self‐assembly of amido groups, which resulted in the formation of a more highly ordered polymeric structure. A novel monomer, bis(3‐methyldimethoxysilylpropyl) terephthalamide ( M ), was prepared by a hydrosilylation reaction in the presence of dicyclopentadienyl platinum dichloride as a catalyst. The structures of the monomer ( M ) and the polymer ( L ) were characterized by Fourier transform infrared, ¹H NMR, ¹³C NMR, ²⁹Si NMR, mass spectrometry, X‐ray diffraction, differential scanning calorimetry, and vapor pressure osmometry. All the characterization data indicated that the synthesized polymer ( L ) possessed an ordered ladderlike structure. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3161–3170, 2002     

Cu (II)‐β‐cyclodextrin complex stabilized on magnetic nanoparticles: A retrievable hybrid promoter for green synthesis of spiropyrans

The magnetic core of manganese ferrite (MnFe₂O₄) nanoparticles has a significant stability in comparison with ferrite (Fe₃O₄) nanoparticles. The unique supramolecular properties of β‐cyclodextrin (β‐CD), such as hydrophobic cavity, hydrophilic exterior and ‐OH functional groups, make it a good candidate for functionalization and catalytic application. So, a surface‐modified magnetic solid support with the Cu (II)‐β‐CD complex was prepared. The structure of nanoparticles was characterized by Fourier transform‐infrared spectroscopy, X‐ray powder diffraction, thermogravimetric analysis, vibrating‐sample magnetometry, inductively coupled plasma‐optical emission spectrometry and scanning electron microscope analyses. The catalytic activity of these nanoparticles was investigated in the synthesis of spiropyrans and high yields of desired products obtained under green media. Some advantages of this novel catalyst for this reaction are high yields, short reaction times, green solvent and conditions, easy workup procedure, negligible copper leaching, reusability without a significant diminish in catalytic efficiency, and simple separation of nanocatalyst by using an external magnet alongside the environmental compatibility and sustainability.     

Non‐surfactant template‐directed synthesis of SiO2‐polyimide hybrid self‐standing films with ordered mesoporous structure

The silica‐PI hybrid self‐standing films with ordered mesoporous structure have been prepared by using dibenzoyl‐L ‐tartaric acid (L ‐DBTA) as non‐surfactant template under mild sol–gel route. Polyimide matrix was obtained from polyamic acid (PAA) via thermal imidization process and the template was removed in this process. The PI‐based hybrid film with 20 wt% SiO₂ obtained from DBTA presented the ordered mesoporous channels with average pore size of about 2.0 nm and BET surface area of 1167 m²/g. FTIR and SEM studies indicated that the hydrogen bond interaction between the carboxylic groups of DBTA and benzamide bonds of PAA made the PAA possibly participate in the assembly process of the aggregates of the non‐surfactant template molecules. The mechanical, thermal and some physical properties of these hybrid films materials were also characterized. Copyright © 2010 John Wiley & Sons, Ltd.