Streamlined Mesoporous Silica Nanoparticles with Tunable Curvature from Interfacial Dynamic-Migration Strategy for Nanomotors
Yuzhu MaKun LanBorui XuLi XuLinlin DuanMengli LiuLiang ChenTiancong ZhaoJunye ZhangZirui LvAhmed A. ElzatahryXiaomin LiDongyuan Zhao
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Streamlined architectures with a low fluid-resistance coefficient have been receiving great attention in various fields. However, it is still a great challenge to synthesize streamlined architecture with tunable surface curvature at the nanoscale. Herein, we report a facile interfacial dynamic migration strategy for the synthesis of streamlined mesoporous nanotadpoles with varied architectures. These tadpole-like nanoparticles possess a big streamlined head and a slender tail, which exhibit large inner cavities (75–170 nm), high surface areas (424–488 m2 g–1), and uniform mesopore sizes (2.4–3.2 nm). The head curvature of the streamlined mesoporous nanoparticles can be well-tuned from ∼2.96 × 10–2 to ∼5.56 × 10–2 nm–1, and the tail length can also be regulated from ∼30 to ∼650 nm. By selectively loading the Fe3O4 catalyst in the cavity of the streamlined silica nanotadpoles, the H2O2-driven mesoporous nanomotors were designed. The mesoporous nanomotors with optimized structural parameters exhibit outstanding directionality and a diffusion coefficient of 8.15 μm2 s–1.Keywords:
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The removal of excess CO2 from the atmosphere is expected to play a major role in the mitigation of global warming. Solid-state adsorbents, consisting of CO2-binding functionalities on porous supports, can provide high CO2 capture capacities with low energy requirements. In this contribution, we report on the vapor-phase functionalization of porous carbon fibers with amine functionalities. Functionalization occurs either via direct exposure to cyclic azasilane molecules (2,2-dimethoxy-1,6-diaza-2-silacyclooctane) or by the atomic layer deposition of Al2O3 followed by exposure to azasilane. XPS analysis and SEM/energy-dispersive x-ray spectroscopy (EDX) measurements confirmed Al2O3 deposition and amine functionalization. Yet, the two different functionalization approaches led to different amine loadings and distinct differences in porosity upon functionalization, which affected CO2 capture. Combining Al2O3 and amine functionalization resulted in fast CO2 sorption with superior capturing efficiency. In contrast, direct functionalization resulted in strong reduction of the surface area of the porous support and limited gas exchange. We attribute the superior capture efficiency to the porosity level achieved when combining Al2O3 and amine functionalization demonstrating that this approach might be valuable for compact high-throughput direct air, CO2 capture systems.
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A thermally induced functionalization process for gallium nitride surfaces with 1-alkenes is introduced. The resulting functionalization layers are characterized with atomic force microscopy and X-ray photoelectron spectroscopy and compared to reference samples without and with a photochemically generated functionalization layer. The resulting layers show very promising characteristics as functionalization for GaN based biosensors. On the basis of the experimental results, important characteristics of the functionalization layers are estimated and a possible chemical reaction scheme is proposed.
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Carbon materials including carbon nanoparticles, such as nanographite, graphene and graphenic materials, and carbon nanotubes are known to be highly hydrophobic. Oxidation treatments are widely used as the best methods to improve their affinity in a liquid medium or a polymer matrix so that they can be dispersed, handled and processed. Here, we have applied eight different oxidation treatments in order to graft oxygen-containing functional groups at the surface of polyhedral graphitic particles synthesized by arc discharge from graphite, also called astralenes. The used functionalization approaches include both standard chemical attack by strong oxidants and radical functionalization of the sp2 network by direct C[double bond, length as m-dash]C bond opening. Commonly efficient functionalization methods were unsuccessful to functionalize astralenes while radicals generated from arylhydrazine could lead to functionalization of the outer surface of astralenes. The occurrence of functionalization could be shown by TGA coupled with MS and XPS. The reported method represents the first example of functionalization of astralenes. The efficiency of the applied functionalization methods is discussed considering the chemical reactivity of different carbon nanomaterials including graphene and carbon nanotubes.
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Abstract This review describes the chemistry of the formation and functionalization of molecularly templated mesoporous silica, as well as applications of functionalized mesoporous silica. The functionalization can be selectively placed on the internal or external surfaces, or even within the pore walls of mesoporous silica. Applications of functionalized mesoporous silica are highlighted on catalysis, sorption and separation, host‐guest synthesis of nanostructured materials and microelectronics.
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Abstract A method for modifying the external surfaces of a series of nanoscale metal–organic frameworks (MOFs) with 1,2‐dioleoyl‐ sn ‐glycero‐3‐phosphate (DOPA) is presented. A series of zirconium‐based nanoMOFs of the same topology (UiO‐66, UiO‐67, and BUT‐30) were synthesized, isolated as aggregates, and then conjugated with DOPA to create stably dispersed colloids. BET surface area analysis revealed that these structures maintain their porosity after surface functionalization, providing evidence that DOPA functionalization only occurs on the external surface. Additionally, dye‐labeled ligand loading studies revealed that the density of DOPA on the surface of the nanoscale MOF correlates to the density of metal nodes on the surface of each MOF. Importantly, the surface modification strategy described will allow for the general and divergent synthesis and study of a wide variety of nanoscale MOFs as stable colloidal materials.
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Modification of nanomaterial surface through functionalization has created a great revolution in the field of nanotechnology specially in the field of pharmaceutical and biomedical sciences. The clinical results have suggested that functionalization of nanoparticles with specific chemical species yielded multifunctional nanoparticles with enhanced efficacy. Precisely engineered, functionalized nanoparticles are finding use as optical materials, components of sensors, catalyst precursors and a host for other applications. Functionalization of host molecules with inorganic/organic functional groups is a useful strategy in the preparation of advanced materials combining the optoelectronic and surface properties of the substrate with the molecular selectivity of the covering groups. Conjugation of these specific chemical functional groups create specific surface sites on nanoparticles with selective molecular attachment to perform specific functions viz. functionalization of gold nanoparticles with amino acids such as lysine, polylysine and glycine etc. bind DNA with higher efficiency for gene delivery without toxicity. Surface-functionalization firstly, links the nanoparticles with various organic and inorganic moieties, secondly, improves the solubility of nanoparticles so that they may be used as carriers for hydrophobic species and thirdly, they can be used for the homogeneous distribution in organic matrix. The surface functionalization can be done by any of the process, either (i) by post-functionalization , in which functionalization is generally done on the already formed inorganic nanoparticles or (ii) by in- situ functionalization, in which functionalization is done during synthesis. The functional groups generally used for tailoring surface functionality are hydroxy-, thio-, amino-, nitro-, carboxy-, or primary alkyl groups etc. The operating forces works for functionalization are mainly hydrophobic, hydrophilic, ionic, nonionic ,van der waal’s or hydrogen bond interactions.
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