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Zn2GeO4-En Hybrid Nanoribbons and Their PMAA Based Composite Nanomaterials: Synthesis, Characterizations and Applications

Author: YuLi
Tutor: HuJunQing
School: Donghua University
Course: Polymer Chemistry and Physics
Keywords: hybrid nanomaterials Zn2GeO4-ethylenediamine hybrid nanoribbons poly-(methacrylic acid) distillation-precipitation polymerization
CLC: TB383.1
Type: Master's thesis
Year: 2012
Downloads: 47
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With the development of nanotechnology, multi-functional inorganic-organic hybrid materials have attracted considerable attention during past few decades, and inorganic-organic hybrid nanomaterials have been widely used in electronics, chemistry, biology, aviation, etc., because of their combination properties of inorganic, organic and nanomaterials. So it is vitally important to discover and study inorganic-organic hybrid nanomaterials that have tremendous fascinating properties.In this paper, synthesis, characterizations and applications of inorganic-organic hybrid nanoribbon (Zn2GeO4-ethylenediamine), inorganic-organic molecules-polymer hybrid nanoribbons (PMAA@Zn2Ge04-ethylenediamine), inorganic-polymers hybrid nanospheres (PMAA@SiO2, and SiO2@PMAA@SiO2) have been totally discussed. The structures and properties of these hybrid nanomaterials were characterized and studied by X-ray diffraction (XRD), Fourier translation infrared (FT-IR), thermogravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS), ionic coupled plasma-atomic emission spectroscopy (ICP-AES). Generally, some achievements within this thesis were listed as follows:(1) Ultralong Zn2GeO4-ethylenediamine hybrid nanoribbons were synthesized by a moderate solvothermal route using ethylenediamine as medium reagent, and their ultralong, ultrathin and temperature resistance properties were confirmed by referred characterizations.(2) Zn2GeO4-ethylenediamine hybrid membranes were produced by self-assembly process with good mechanical and recyclable properties, high selectivity and adsorption capacity. In the binary mixture systems contain Pb2+/Cu2+、Pb2+/Cd2+、Pb2+/Co2+、Cu2+/Cd2+、Cu2+/Co2+、Cd2+/Co2+, and ternary mixtures such as Pb2+/Cu2+/Cd2+、Pb2+/Cu2+/Co2+、Pb2+、Cd2+/Co2+、Cu2+/Cd2+/Co2+, and in Pb2+/Cu2+/Cd2+/Co2+ mixture systems, the membranes showed high adsorption capacity to Pb2+. With the increase of the concentration of heavy metal ions, the adsorption efficiency also increased, namely, ranging from 58.7 to 71.3 and 74.6 mg g-1 with the initial concentration increasing from 2.5 to 5.0 and 10 mM under condition of 15℃within one hour. When disodium EDTA used as an eluent, the desorption efficiency of the membrane can reach as high as 94%, that’s exactly why it showed good recyclability. Mechanism of adsorption and desorption process indicate that its adsorption properties of heavy metals can be attributed to their organic ethylenediamine molecules which have chelation effect, suggesting that lots of-NH2 groups in EDA molecules within the hybrid nanoribbons have an intimate contact with metal ions. e.g., Pb2+, in solutions; however, when the membranes were eluted by the disodium EDTA solution, stronger coordination ligands in the disodium EDTA would have a stronger bonding with Pb2+, made Pb2+ easily desorb from the membranes.(3) We first successfully synthesized inorganic-organic molecules-polymer hybrid nanoribbons (PMAA@Zn2GeO4-ethylenediamine) by radical polymerization method using methacrylic acid (MAA) as monomer, azobisisobutyronitrile (AIBN) as initiator, ethylene glycol dimethacrylate (EGDMA) as crosslinking agent. This simple and easy method provides a new synthesis and research access to other similarly important functional hybrid nanomaterials.(4) SiO2 nanospheres were firstly modified by 3-(trimethoxysilyl) propylmethacrylate and then their external surfaces were coated with a layer of functional polymer PMAA by distillation-precipitation polymerization method, forming a PMAA@SiO2 nanospheres structure. Secondly, novel SiO2@PMAA@SiO2 yolk-shell structure nanoparticles were obtained by sol-gel route using PMAA@SiO2 nanospheres as precursor, and their microstructures and compositions were thoroughly characterized. These nanomaterials are expected to be used in drug delivery.

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