Functional Material Systems Based on Soft Cages

Discrete molecular soft cages integrate multiple functionalities in one molecule. They express their functions from the confined space in their cavity, functional groups in the cavity interior wall and exterior wall, and the chelating nodes in many chelating cages. Such functional integrity render cage molecules special applications in material engineering. Increasing applications of cage molecules in material design have been reported in recent years. Compared with other cavity-rich molecular structures such as metal-organic framework (MOF) or covalent organic frameworks (COF), discrete soft cages present the unique advantage of material design flexibility, that they can easily composite with nanoparticles or polymers and exist in materials of various forms. We document the development of cage-based materials in recent years and expect to further inspire materials engineering to integrate contribution from the functionality specificity of cage molecules and ultimately promote the development of functional materials and thus human life qualities.     

分子筛限域金属纳米粒子及其氧化还原反应应用的研究进展

沸石分子筛是一类孔隙均匀、结晶度高、结构多样、比表面积大的材料,在催化、分离、吸附等方面得到了广泛的应用。沸石分子筛已被证明是金属纳米粒子(MNPs)的理想载体。金属纳米粒子@沸石分子筛催化剂不仅表现出优异的催化活性,而且具有较高的稳定性和择形催化性。此外,限域的金属纳米粒子与具有活性位点的纳米孔骨架的协同作用可以进一步提高复合催化剂的催化活性。金属纳米粒子@沸石分子筛催化剂由于具有较高的活性、择形性和热稳定性等优点,在工业相关应用中引起了人们的极大关注。本文综述了金属纳米粒子@沸石分子筛催化剂的研究进展,重点介绍了多种合成方法以及其在氢化和氧化反应中的应用进展。指出了金属纳米粒子@沸石分子筛催化剂领域存在的问题和挑战并对其未来发展进行展望。     

贵金属复合纳米粒子的研究进展

贵金属复合纳米粒子具有不同于单组分纳米粒子的独特的光、电和催化等物理与化学性能,是构筑新型功能复合材料的重要单元,在传感器、光学材料、催化剂及生物领域都有着重要应用,已成为当前纳米材料科学研究领域中的前沿和热点。本文主要评述了具有核壳、异质结构以及合金结构的贵金属复合纳米粒子的制备、物理与化学性能及应用等方面的研究进展。     

Synthesis of silver nanoparticles with different shapes

Today the synthesis of silver nanoparticles is very common due to their numerous applications in various fields. Silver nanoparticles have unique properties such as: optical and catalytic properties, which, depend on the size and shape of the produced nanoparticles. So, today the production of silver nanoparticles with different shapes which have various uses in different fields such as medicine, are noted by many researchers. This article, is an attempt to present an overview of the shape-controlled synthesis of silver nanoparticles using various methods.     

Outstanding Catalytic Activity of Ultra‐Pure Platinum Nanoparticles

Small (4 nm) nanoparticles with a narrow size distribution, exceptional surface purity, and increased surface order, which exhibits itself as an increased presence of basal crystallographic planes, can be obtained without the use of any surfactant. These nanoparticles can be used in many applications in an as‐received state and are threefold more active towards a model catalytic reaction (oxidation of ethylene glycol). Furthermore, the superior properties of this material are interesting not only due to the increase in their intrinsic catalytic activity, but also due to the exceptional surface purity itself. The nanoparticles can be used directly (i.e., as‐received, without any cleaning steps) in biomedical applications (i.e., as more efficient drug carriers due to an increased number of adsorption sites) and in energy‐harvesting/data‐storage devices.     

Paper surfaces functionalized by nanoparticles

Nanomaterials with unique electronic, optical and catalytic properties have recently been at the forefront of research due to their tremendous range of applications. Taking gold, silver and titania nanoparticles as examples, we have reviewed the current research works on paper functionalized by these nanoparticles. The functionalization of paper with only a very small concentration of nanoparticles is able to produce devices with excellent photocatalytic, antibacterial, anti-counterfeiting, Surface Enhanced Raman Scattering (SERS) and Surface Plasmon Resonance (SPR) performances. This review presents a brief overview of the properties of gold, silver and titania nanoparticles which contribute to the major applications of nanoparticles-functionalized paper. Different preparation methods of the nanoparticles-functionalized paper are reviewed, focusing on their ability to control the morphology and structure of paper as well as the spatial location and adsorption state of nanoparticles which are critical in achieving their optimum applications. In addition, main applications of the nanoparticles-functionalized papers are highlighted and their critical challenges are discussed, followed by perspectives on the future direction in this research field. Whilst a few studies to date have characterized the distribution of nanoparticles on paper substrates, none have yet optimized paper as a nanoparticles' substrate. There remains a strong need to improve understanding on the optimum adsorption state of nanoparticles on paper and the heterogeneity effects of paper on the properties of these nanoparticles.     

Porous Carbon Nitride Frameworks Derived from Covalent Triazine Framework Anchored Ag Nanoparticles for Catalytic CO2 Conversion

Porous carbon nitride frameworks (PCNFs) with uniform and rich nitrogen dopants and abundant porosity were successfully fabricated through the direct carbonization of the covalent triazine frameworks (CTFs) at different pyrolysis temperatures and used as supports to anchor and stabilize Ag nanoparticles (NPs) for catalytic CO₂ conversion. Importantly, the pyrolysis temperature plays a crucial role in the properties of porous carbon nitride frameworks. The material carbonized at 700 °C showed the highest surface area and micro- and mesoporous structure with a certain interlayer distance. Taking advantage of their unique surface characteristics, PCNF-supported Ag NP catalysts (Ag/PCNF-T, T=pyrolysis temperature) were prepared by a simple chemical method. A series of characterizations revealed that Ag NPs are embedded in the porous carbon nitride frameworks and confined to a relatively small size with high dispersion owing to the assistance of the abundant surface groups and porous structures. The as-obtained Ag/PCNF-T catalysts, especially Ag/PCNF-700, showed excellent catalytic activity, selectivity, and stability for the carboxylation of CO₂ with terminal alkynes under mild conditions. This can be due to the existence of abundant nitrogen atoms and diverse porosity, which resulted in highly efficient catalytic activity and stability.     

Organic reactions of monolayer-protected metal nanoparticles

This paper presents a concise review of various organic reactions of monolayer-protected metal nanoparticles, with an emphasis on their current applications. Organic reactions of monolayer-protected nanoparticles lead to the functionalized nanoparticles, which exhibit interesting properties such as catalytic, electrochemical, photoresponsive, chemical sensing, and biocompatible properties. To cite this article: D.K.P. Ng, C. R. Chimie 6 (2003).     

Toward monodispersed silver nanoparticles with unusual thermal stability

A novel in situ autoreduction route has been developed, by which monodispersed silver nanoparticles with tunable sizes could be easily fabricated on silica-based materials, especially inside the channels of mesoporous silica (MPS). 13C CP/MAS NMR spectroscopy was employed to monitor the whole assembly process. It was demonstrated that the amino groups of APTS (aminopropyltriethoxyl silane)-modified MPS can be used to anchor formaldehyde to form novel reducing species (NHCH2OH), on which Ag(NH3)2NO3 could be in situ reduced. Monodispersed silver nanoparticles were thus obtained. In situ XRD and in situ TEM experiments were used to investigate and compare the thermal stabilities of silver nanoparticles on the external surface of silica gels (unconfined) and those located inside the channels of SBA-15 (confined). It was observed that unconfined silver nanoparticles tended to agglomerate at low temperatures (i.e., lower than 773 K). The aggregation of silver nanoparticles became more serious at 773 K. However, for those confined silver nanoparticles, no coarsening process was observed at 773 K, much higher than its Tammann temperature (i.e., 617 K). Only when the treating temperature was higher than 873 K could the agglomeration of those confined silver nanoparticles happen with time-varying via the Ostwald ripening process. The confinement of mesopores played a key role in improving the thermal stabilities of silver nanoparticles (stable up to 773 K without any observable coarsening), which is essential to the further investigations on their chemical (e.g., catalytic) properties.     

Biocompatible heterostructured nanoparticles for multimodal biological detection

Hybrid nanoparticles are of significant interest primarily because of their innate multifunctional capabilities. These capabilities can be exploited when hybrid nanoparticles are used for applications in the biomedical sciences in particular, where they are utilized as multimodal nanoplatforms for sensing, imaging, and therapy of biological targets. However, the realization of their biomedical applications has been difficult, in part because of a lack of high quality hybrid nanoparticles which possess high aqueous colloidal stability and biocompatibility while retaining their multifunctionalities. Here, we present the development of inorganic heterodimer nanoparticles of FePt-Au with multifunctional capabilities including catalytic growth effects, magnetic resonance (MR) contrast effects, optical signal enhancing properties, and high colloidal stability and biocompatibility. Their multimodal capabilities for biological detection are demonstrated through their utilizations in the patterned biochip based detection of avidin-biotin interaction as well as in molecular MR imaging of neuroblastoma cells.     

Catalytic activity of TiO2 nanoparticles in the synthesis of some 2,3-disubstituted dihydroquinazolin-4（1H）-ones

Green chemistry is playing an important role for synthesizing organic compounds, due to its eco-friendly nature and low cost. In green chemistry, metal nanoparticles exhibited some useful physical and chemical properties （catalytic activity）. Due to its diverse properties, nanoparticles can be utilized as a catalyst in various organic reactions. Recent research has been directed towards the utilization of eco- friendly and bio-friendly plant materials in nanoparticles synthesis. In our present work, TiO2 nanoparticles （TiO2 NPs） were synthesized using Annona squamosa peel extract and their catalytic applications were studied on the 2,3-disubstituted dihydroquinazolin-4（l1H）-one synthesis. Synthesized compounds were confirmed using FT-IR.1H NMR, 13C NMR and GC-MS analyses.     

Integrated nanoparticle-biomolecule hybrid systems: synthesis, properties, and applications

Nanomaterials, such as metal or semiconductor nanoparticles and nanorods, exhibit similar dimensions to those of biomolecules, such as proteins (enzymes, antigens, antibodies) or DNA. The integration of nanoparticles, which exhibit unique electronic, photonic, and catalytic properties, with biomaterials, which display unique recognition, catalytic, and inhibition properties, yields novel hybrid nanobiomaterials of synergetic properties and functions. This review describes recent advances in the synthesis of biomolecule-nanoparticle/nanorod hybrid systems and the application of such assemblies in the generation of 2D and 3D ordered structures in solutions and on surfaces. Particular emphasis is directed to the use of biomolecule-nanoparticle (metallic or semiconductive) assemblies for bioanalytical applications and for the fabrication of bioelectronic devices.     

Photoinitiated Energy Transfer in Porous-Cage-Stabilised Silver Nanoparticles

We report a new composite material consisting of silver nanoparticles decorated with three-dimensional molecular organic cages based on light-absorbing porphyrins. The porphyrin cages serve to both stabilize the particles and allow diffusion and trapping of small molecules close to the metallic surface. Combining these two photoactive components results in a Fano-resonant interaction between the porphyrin Soret band and the nanoparticle-localised surface-plasmon resonance. Time-resolved spectroscopy revealed the silver nanoparticles transfer up to 37 % of their excited-state energy to the stabilising layer of porphyrin cages. These unusual photophysics cause a 2-fold current increase in photoelectrochemical water-splitting measurements. The composite structure provides a compelling proof of concept for advanced photosensitiser systems with intrinsic porosity for photocatalytic and sensing applications.     

Electrochemical synthesis and properties of gold nanomaterials

Approximately two decades ago, gold catalyst opened up a new view of their properties when they are introduced in the form of nanomaterials, since at that time, many approaches to preparation and use of gold nanoparticles started to be used in many practical applications. Today, the research activity relating to gold nanomaterials is becoming systematic and goes further to make connections between their surface structure, chemical and physical properties, and possible applications. Since electrodeposition is one of the most controllable methods used to prepare nanoparticles, nanowires, and nanoclusters of gold, the present review gives preference on their electrochemical synthesis. The relationship between catalytic activity, size, morphology and stability of gold nanomaterials is discussed in detail. Based on the properties of the prepared gold nanocatalysts, their new applications in chemical, photochemical, and electrochemical reactions have been observed.     

A Honeycomb-Like Bulk Superstructure of Carbon Nanosheets for Electrocatalysis and Energy Storage

Superstructures have attracted extensive attention because of their potential applications in materials science and biology. Herein, we fabricate the first centimeter-sized porous superstructure of carbon nanosheets (SCNS) by using metal–organic framework nanoparticles as a template and polyvinylpyrrolidone as an additional carbon source. The SCNS shows a honeycomb-like morphology with wall-sharing carbon cages, in each cavity of which a porous carbon sphere is encapsulated. A single piece of SCNS is directly used as the electrode for a two-electrode symmetrical supercapacitor cell without any binders and supports, benefiting from its advantage in ultra-large geometric size, and the Fe-immobilized SCNS exhibits excellent catalytic performances for oxygen reduction reaction and in a Zn–air battery. This synthetic strategy presents a facile approach for preparing functional SCNS at centimetric scale with controllable morphologies and compositions favoring the fabrication of energy devices.     

Non-enzyme entrapping biohydrogels in catalysis

This review provides an overview of the current status and future directions of the use of biohydrogels (i.e., hydrogels obtained from biopolymers) as heterogeneous catalysts and/or supports for catalytic metal nanoparticles. This review collects a wide variety of biohydrogels used in catalytic applications, including gels made of polysaccharides (chitosan, alginate, carrageenan, dextran, agarose), proteins (gelatin, silk fibroin, ferritin) and nucleic acids (DNA). Additionally, the most significant features about the recyclability of these materials, their structural properties and the type of reactions that they catalyze are discussed.     

Mass Production and Pore Size Control of Holey Carbon Microcages

Architectural control of porous solids, such as porous carbon cages, has received considerable attention for versatile applications because of their ability to interact with liquids and gases not only at the surface, but throughout the bulk. Herein we report a scalable, facile spray‐pyrolysis route to synthesize holey carbon microcages with mosquito‐net‐like shells. Using the surfaces of water droplets as the growth templates, styrene–butadiene rubber macromolecules are controllably cross‐linked, and size‐controllable holes on the carbon shells are generated. The as‐formed carbon microcages encapsulating Si nanoparticles exhibit enhanced lithium‐storage performances for lithium‐ion batteries. The scalable, inexpensive synthesis of porous carbon microcages with controlled porosity and the demonstration of outstanding electrochemical properties are expected to extend their uses in energy storage, molecular sieves, catalysis, adsorbents, water/air filters, and biomedical engineering.     

石墨烯量子点负载银纳米粒子制备及氧还原电催化活性

银基氧还原电催化剂具有较高的电催化活性且价格相对低廉,因而受到广泛关注. 本文采用简单、预先合成的石墨烯量子点作为载体和还原剂,制得了负载于石墨烯量子点、且无保护剂和表面活性剂的表面洁净银纳米粒子（Ag NPs/GQDs）. 电化学研究表明,Ag NPs/GQDs复合电催化剂的氧还原有较高的电催化活性,氧在碱性溶液中可经4电子途径还原为水. 与商业铂碳电极（Pt/C）相比,AgNPs/GQDs电极具有高催化电流密度、良好稳定性和极佳抗甲醇性能. 该银纳米粒子对开发高性能和低成本的非铂氧还原电催化剂有潜在的应用前景.     

Cu‐Based Nanoparticles as Emerging Environmental Catalysts

This account provides an overview of current research activities on nanoparticles containing the earth‐abundant and inexpensive element copper (Cu) and Cu‐based nanoparticles, especially in the field of environmental catalysis. The different synthetic strategies with possible modification of the chemical/ physical properties of these nanoparticles using such strategies and/or conditions to improve catalytic activity are presented. The design and development of support and/or bimetallic systems (e. g., alloys, intermetallic, etc.) are also included. Herein, we report synthetic approaches of Cu and Cu‐based nanoparticles (monometallic copper, bimetallic copper and copper (II) oxide nanoparticles/nanostructures) and impregnation of such nanoparticles onto support material (e. g., Co₃O₄ nanostructure), along with their applications as environmental catalyst for various oxidation and reduction reactions. Finally, this account provides necessary advances and perspectives of Cu‐based nanoparticles in the environmental catalysis.     

Silica‐Coated Metal Nanoparticles

The advanced high‐quality synthesis of dense and porous silica‐coated nanostructures is enjoying ever‐increasing research interests for their important properties and diverse applications, especially for catalytic, controlled release, colorimetric diagnostics, photothermal therapy, surface enhanced Raman scattering (SERS) detection, and so forth. In this timely Focus Review, we summarize the up‐to‐date synthesis strategies, improved properties, and emerging applications of silica‐coated metal nanoparticles. In particular, the large scale synthesis of silica‐coated metal nanoparticles and the recent development of hollowed‐out silica‐coated metal nanoparticles by silica dissolution are emphasized for new and practical applications.