Design of Hollow Nanoreactors for Size- and Shape-Selective Catalytic Semihydrogenation Driven by Molecular Recognition

Mimicking the structures and functions of cells to create artificial organelles has spurred the development of efficient strategies for production of hollow nanoreactors with biomimetic catalytic functions. However, such structure are challenging to fabricate and are thus rarely reported. We report the design of hollow nanoreactors with hollow multishelled structure (HoMS) and spatially loaded metal nanoparticles. Starting from a molecular-level design strategy, well-defined hollow multishelled structure phenolic resins (HoMS-PR) and carbon (HoMS-C) submicron particles were accurately constructed. HoMS-C serves as an excellent, versatile platform, owing to its tunable properties with tailored functional sites for achieving precise spatial location of metal nanoparticles, internally encapsulated (Pd@HoMS-C) or externally supported (Pd/HoMS-C). Impressively, the combination of the delicate nanoarchitecture and spatially loaded metal nanoparticles endow the pair of nanoreactors with size–shape-selective molecular recognition properties in catalytic semihydrogenation, including high activity and selectivity of Pd@HoMS-C for small aliphatic substrates and Pd/HoMS-C for large aromatic substrates. Theoretical calculations provide insight into the pair of nanoreactors with distinct behaviors due to the differences in energy barrier of substrate adsorption. This work provides guidance on the rational design and accurate construction of hollow nanoreactors with precisely located active sites and a finely modulated microenvironment by mimicking the functions of cells.     

Size‐controlled synthesis of soluble‐conjugated microporous polymer nanoparticles through sonogashira polycondensation in confined nanoreactors

Soluble conjugated polymeric nanoparticles were synthesized through Sonogashira polycondensation between different combinations of multifunctional alkynes and aryl halides in structurally well‐defined mesoporous reactors. The growth of the polymeric nanoparticles was controlled by the spatial confinement of the nanoreactors, giving conjugated polymeric nanoparticles with narrow size distribution centered at 5 nm. All the obtained polymers are freely soluble in common solvents and can be fabricated into thin film. Both of the solution and thin film prepared from these polymeric nanoparticles were highly fluorescent, endowing them potential applications in light emitting and other optoelectronic fields. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2285–2290     

Palladium-Carbon Composite Nanoparticle Films with Enhanced Electrocatalytic Activity for Hydrogen Peroxide Sensors

A nanocomposite electrocatalyst was prepared with the method of cluster beam deposition of palladium nanoparticle thin lms on carbon nanoparticle supporting layers and used as sensitive nonenzyme hydrogen peroxide sensors. An enhancement on the electrocatalytic activity of the palladium nanoparticles toward H₂O₂ reduction was observed, which was related to the coverage of the carbon nanoparticles. With one monolayer of carbon nanoparticles, the H₂O₂ detection sensitivity reached the maximum, which was more than twice of that of the pure Pd nanoparticles.     

Size‐Controlled Synthesis of Conjugated Polymer Nanoparticles in Confined Nanoreactors

Soluble conjugated polymeric nanoparticles are synthesized by Suzuki‐type polycondensation of two monomers (A_x + B_y, x>2, y≥2) in the channel of ordered mesoporous silica‐supported carbon nanomembranes (nanoreactors). These synthesized soluble conjugated microporous polymers (SCMPs) exhibit uniform particle‐size distributions and well‐controlled particle sizes. The control of particle size stems from the fact that the polycondensations exclusively take place inside the mesochannels of the nanoreactors. Photoluminescence studies show that polymeric nanoparticles with tetraphenylethene and pyrene substructures are highly fluorescent. The combination of both physical stability and processability offered by the soluble polymeric nanoparticles makes them particularly attractive in light emitting and other optoelectronic applications.     

Hollow Carbon Sphere Nanoreactors Loaded with PdCu Nanoparticles: Void-Confinement Effects in Liquid-Phase Hydrogenations

Nanoreactors with hollow structures have attracted great interest in catalysis research due to their void-confinement effects. However, the challenge in unambiguously unraveling these confinement effects is to decouple them from other factors affecting catalysis. Here, we synthesize a pair of hollow carbon sphere (HCS) nanoreactors with presynthesized PdCu nanoparticles encapsulated inside of HCS (PdCu@HCS) and supported outside of HCS (PdCu/HCS), respectively, while keeping other structural features the same. Based on the two comparative nanoreactors, void-confinement effects in liquid-phase hydrogenation are investigated in a two-chamber reactor. It is found that hydrogenations over PdCu@HCS are shape-selective catalysis, can be accelerated (accumulation of reactants), decelerated (mass transfer limitation), and even inhibited (molecular-sieving effect); conversion of the intermediate in the void space can be further promoted. Using this principle, a specific imine is selectively produced. This work provides a proof of concept for fundamental catalytic action of the hollow nanoreactors.     

碳纳米粒子支撑的钯纳米催化剂在甲酸氧化中的电催化活性

采用化学还原法制备了碳纳米粒子支撑的钯纳米结构(Pd-CNP). 透射电镜表征显示在Pd-CNP纳米复合物中,金属Pd呈菜花状结构,粒径约20~30 nm。它们由许多更小的Pd纳米粒子（3~8 nm）组成. 电化学研究表明,虽然Pd-CNP的电化学活性面积比商业Pd黑低40%（可能原因是部分Pd表面被一层碳纳米粒子覆盖）,但其对甲酸氧化却表现出更好的电催化活性：质量比活性和面积比活性都比Pd黑高几倍. 催化活性增强的原因可能是碳纳米粒子支撑的Pd纳米结构具有特殊的层次化结构,可以形成更多的活性位,以及表面位更利于反应进行.     

Electrodeposition and characterization of Pd nanoparticles doped amorphous hydrogenated carbon films

Palladium (0) nanoparticles incorporated hydrogenated amorphous carbon (Pd/a-C:H) films were synthesized on single crystal silicon (100) substrates by electrochemical deposition route using methanol and camphor as carbon source, and Pd nanoparticles as dopant. The characterization results indicate that Pd nanocrystalline particles with diameter in the range of 1–5 nm dispersed in the amorphous carbon matrix. Compared with pure a-C:H films, the introduction of Pd nanoparticles didn't change the structure of carbon films. At the end, the growth mechanism of the Pd/a-C:H composite films was discussed.     

Catalytic activity and regeneration property of a Pd nanoparticle encapsulated in a hollow porous carbon sphere for aerobic alcohol oxidation

A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions.     

Nanoscale Magnetic Stirring Bars for Heterogeneous Catalysis in Microscopic Systems

Nanometer‐sized magnetic stirring bars containing Pd nanoparticles (denoted as Fe₃O₄‐NC‐PZS‐Pd) for heterogeneous catalysis in microscopic system were prepared through a facile two‐step process. In the hydrogenation of styrene, Fe₃O₄‐NC‐PZS‐Pd showed an activity similar to that of the commercial Pd/C catalyst, but much better stability. In microscopic catalytic systems, Fe₃O₄‐NC‐PZS‐Pd can effectively stir the reaction solution within microdrops to accelerate mass transfer, and displays far better catalytic activity than the commercial Pd/C for the hydrogenation of methylene blue in an array of microdroplets. These results suggested that the Fe₃O₄‐NC‐PZS‐Pd could be used as nanoscale stirring bars in nanoreactors.     

Pd@tetrahedral hollow magnetic nanoparticles coated with N‐doped porous carbon as an efficient catalyst for hydrogenation of nitroarenes

Hollow magnetic nanoparticles (MNPs) with tetrahedral morphology were synthesized and then covered by a shell prepared by coating with melamine–formaldehyde followed by the introduction of glucose‐derived carbon. Subsequently, Pd nanoparticles were immobilized and the core–shell nanocomposite was carbonized. The obtained magnetic catalyst was successfully applied for the hydrogenation of nitroarenes in aqueous media. To investigate the effects of the morphology of MNPs, the nature of carbon shell, and the order of incorporation of Pd nanoparticles, several control catalysts, including the MNPs with different morphologies (disc‐like and cylinder); MNPs coated with different shells (sole glucose‐derived carbon or melamine–formaldehyde carbon shell); and a nanocomposite, in which Pd was immobilized after carbonization, were prepared and examined as catalyst for the model reaction. To justify the observed different catalytic activities of the catalysts, their Pd loadings, leaching, and specific surface areas were compared. The results confirmed that tetrahedral MNPs coated with porous N‐rich carbon shell exhibited the best catalytic activity. The high catalytic activity of this catalyst was attributed to its high surface area and the interaction of N‐rich shell with Pd nanoparticles that led to the higher Pd loading and suppressed Pd leaching.     

Interactions of O(2) with Pd nanoparticles on alpha-Al(2)O(3)(0001) at low and high O(2) pressures

The interaction of O(2) with small Pd particles (2-10 nm) supported on an alpha-Al(2)O(3)(0001) single crystal under both ultrahigh vacuum (UHV) and high-pressure conditions has been studied by temperature-programmed desorption (TPD), temperature-programmed low-energy ion scattering (TP-LEIS), and X-ray photoelectron spectroscopy (XPS). A low O(2) exposure (30 L) at 500 K leads to surface oxygen adatoms on the Pd nanoparticles, which desorb in TPD as O(2) in a peak at approximately 880 K. Surface O adatoms on the smallest Pd particles move to subsurface sites starting at 400 K, and they almost all move subsurface by approximately 750 K, desorbing mainly at considerably higher temperature. The dominant oxygen species above 700 K is subsurface, implying that it is more stable than oxygen adatoms on Pd. Exposures of the Pd nanoparticles to 25 Torr O(2) at 373-473 K readily convert the Pd to a species whose Pd XPS peak shifts by the same amount as the binding energy difference between bulk Pd and bulk PdO. We attribute this to PdO nanoparticles (or a thin film of PdO on or under the Pd for the larger particles). The decomposition of the PdO on these nanoparticles to Pd in an equilibrium O(2) pressure of 10-7 Torr does not occur until approximately 750 K, or approximately 200 K higher than the equilibrium decomposition of bulk PdO. This is attributed to the higher energy of Pd nanoparticles compared to bulk Pd and, for the larger particles, to the adhesion energy of the PdO film to the Pd, both of which stabilize the PdO on these Pd nanoparticles relative to bulk PdO. This PdO-like film on the larger particles may be similar to the ordered oxide thin film previously reported to form on Pd(111) but may also reside at the alpha-Al(2)O(3) interface and be partially stabilized by adhesion to this interface.     

Reactivity of palladium nanoparticles supported on a microemulsion-based organogel network in supercritical carbon dioxide

Palladium (Pd) nanoparticles were prepared using the phase transfer method and coated with alkylamines as stabilizing agents stably dispersed in nonpolar solvents. Spherical Pd nanoparticles with an average diameter of 4 nm and a relatively narrow size distribution were obtained using hexylamine or dodecylamine, and they were successfully incorporated in microemulsion-based gelatin organogel (OG); also, an OG network containing Pd nanoparticles was prepared via drying. For the Mizoroki-Heck cross-coupling reaction of iodobenzene with methyl acrylate in supercritical carbon dioxide, the Pd nanoparticles in the OG network exhibited much higher reactivity than those in powder state. Preparation conditions of OG (e.g., gelatin concentration) affected the apparent reactivity of the supported Pd nanoparticles. The Pd nanoparticles in the OG network with high gelatin concentration were recycled with no appreciable change of reactivity. In contrast, the reactivity of the Pd nanoparticles with low gelatin concentration decreased during recycling.     

Size‐Tunable Polymeric Nanoreactors for One‐Pot Synthesis and Encapsulation of Quantum Dots

Hydrophilic polymeric nanoparticles are synthesized through a Bergman cyclization‐ mediated intramolecular chain collapse of structurally well‐defined linear polymers, and then used as size‐tunable nanoreactors to fabricate and encapsulate quantum dots in a one‐pot reaction. Crystalline quantum dots are formed in all of these nanoreactors and visualized by transmission electron microscopy. Smaller nanoreactors produce one quantum dot each while larger nanoreactors form a number, resulting in fluorescence quenching. By controlling the molecular weight of the linear polymer precursor, a variable number of nanocrystals are fabricated and assembled in a single nanoreactor.     

纳米碳纤维负载钯催化剂在Heck反应中的应用——载体相互作用的影响

使用多元醇还原法制备了均匀分散的钯纳米颗粒.将钯纳米颗粒负载于板式、鱼骨式和管式纳米碳纤维,得到稳定、可重复使用的非均相催化剂.实验结果表明,钯纳米胶粒同载体之间的电位差对钯在载体上的负载量、粒子大小以及Heck反应中钯的溶失量有很大的影响.在制备过程中,增加钯纳米胶粒同纳米碳纤维表面的电位差能够大大降低钯在Heck反应中的流失.催化剂的反应活性随钯粒子的增大而降低.     

先进蛋黄-蛋壳结构能源转化纳米反应器

蛋黄-蛋壳结构独特的纳米结构及特性,使其在很多领域中具有潜在的应用价值,因此近年来受到了广泛关注.本综述总结了使用蛋黄-蛋壳纳米结构作为纳米反应器的研究进展.从合成策略出发,主要强调最近五年合成蛋黄-蛋壳纳米结构的最新研究进展.通过光催化,甲烷重整和电催化等反应作为典型的反应过程,重点讨论蛋黄-蛋壳结构纳米反应器在催化领域的应用,并对该领域未来的发展进行了展望.     

Development of an Electrochemical Sensor Nanoarray for Hydrazine Detection Using a Combinatorial Approach

The combinatorial screening of different metallic nanoparticles as electrocatalysts was investigated and efficiently applied for the detection of hydrazine. In a first step, glassy carbon microspheres decorated with metallic nanoparticles (Au, Pd, and Ag) were abrasively attached on the surface of a basal plane pyrolytic electrode giving a ‘multi–metal’ nanoarray. In a second step, electrodes modified with only one type of metallic nanoparticles allowed the identification of Pd as the unique catalytic material. In addition, a carbon‐epoxy composite electrode loaded with the Pd nanoparticles was then constructed for a practical use. The carbon‐epoxy composite nanoarray electrode was found to have excellent characteristics as for the sensing of hydrazine with a limit of detection of 2 μM.     

One‐Pot Synthesis of Carbon‐Supported Dendritic Pd‐Au Nanoalloys for Electrocatalytic Ethanol Oxidation

One‐pot synthesis of carbon‐supported Pd‐Au alloy nanoparticles with well‐defined dendritic shape (Pd‐Au_den/C) was achieved by co‐reduction of K₂PdCl₄/HAuCl₄ mixtures in a molar ratio of 1:1 with hydrazine in the presence of Vulcan XC‐72R. The prepared Pd‐Au_den/C exhibited significantly enhanced performance in the electrocatalytic oxidation of ethanol compared with dendritic Pd nanoparticles and a commercial Pd/C catalyst. Pd‐Au_den/C even showed higher durability in electro‐oxidation of ethanol than the supported catalyst prepared by the deposition of presynthesized dendritic Pd‐Au nanoparticles on the carbon support. The experimental results clearly indicate that enhanced interaction between nanoparticle catalysts and carbon support through the one‐pot synthesis protocol can improve the durability of the electrocatalysts.     

Efficient anchorage of Pd nanoparticles on carbon nanotubes as a catalyst for hydrazine oxidation

A simple method is devised to deposit well-dispersed Pd nanoparticles on multi-walled carbon nanotubes (CNTs). Pd nanoparticles (1–3 nm) prepared in ethanol were transferred to toluene solution and modified by organic molecule benzyl mercaptan which acts as a cross linker between Pd nanoparticles and CNTs. The morphology and structure of the resulting Pd/CNT nanocomposite were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results show that Pd nanoparticles were highly dispersed and effectively anchored on CNTs. The excellent electrocatalytic activity of the Pd/CNT nanocomposite for the oxidation of hydrazine was demonstrated by cyclic voltammetry.     

PtPd-nanoparticles supported by new carbon materials

Nanocomposites based on PtPd nanoparticles with chemical ordering like disordered solid solution on surface of multilayer graphene have been prepared through thermal shock of mechanically obtained mixture of double complex salt [Pd(NH₃)₄][PtCl₆] and different carbon materials–exfoliated graphite, graphite oxide and graphite fluoride. An effect of original carbon precursors on formation of PtPd bimetallic nanoparticles was studied using X-ray absorption spectroscopy (XAFS), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). It was shown that the distribution of bimetallic nanoparticles over the multilayer graphene surface as well as the particles size distribution is controlled by the graphene precursors. For all nanocomposites, the surface of the nanoparticles was found to be Pd-enriched. In case when the thermal exfoliated graphite and graphite oxide were used as the graphene precursors a thin graphitized layer covered the nanoparticles surface. Such a graphitized layer was not observed in the nanocomposite, which used the fluorinated graphite as the precursor.     

Electrochemical fabrication of two-dimensional palladium nanostructures as substrates for surface enhanced Raman scattering

Two-dimensional palladium (Pd) nanostructures have been fabricated by electrochemical deposition of Pd onto an indium tin oxide glass substrate modified with a thin flat film of polypyrrole or a nanofibril film of polyaniline. The experimental results demonstrated that the morphology of Pd nanoparticles strongly depended on the properties of conducting polymers and the conditions of electrochemical deposition. Two-dimensional nanostructures composed of flower-like (consisting of staggered nanosheets) or pinecone-like Pd nanoparticles were successfully synthesized. They can be used as substrates for surface-enhanced Raman scattering after partly decomposing the polymer components by heating in air, and the enhancement factor of the substrate composed of flower-like Pd nanoparticles was measured to be as high as 105 for 4-mercaptopyridine.