METAL NANOPARTICLES FUNCTIONALIZED WITH METAL-LIGAND COVALENT BONDS
- Author(s): Kang, Xiongwu
- Advisor(s): Chen, Shaowei
- et al.
Metal-organic contact has been recognized to play important roles in regulation of optical and electronic properties of nanoparticles. In this thesis, significant efforts have been devoted into synthesis of ruthenium nanoparticles with various metal-ligand interfacial linkages and investigation of their electronic and optical properties.
Ruthenium nanoparticles were prepared by the self-assembly of functional group onto bare Ru colloid surface. As to Ru-alkyne nanoparticles, the formation of a Ru-vinylidene (Ru=C=CH-R) interfacial bonding linkage was confirmed by the specific reactivity of the nanoparticles with imine derivatives and olefin at the metal-ligand interface, as manifested in NMR, photoluminescence, and electrochemical measurements. Interestingly, it was found the electronic coupling coefficient (&beta)for strongly depend upon such metal-ligand interfacial bonding.
Next, such metal-ligand interfacial bonding was extended to ruthenium-nitrene &pi bonds on ruthenium colloids, which were investigated by XPS. The nanoparticles exhibited a 1:1 atomic ratio of nitrogen to sulfur, consistent with that of sulfonyl nitrene fragments. In addition, the nanoparticle-bound nitrene moieties behaved analogously to azo derivatives, as manifested in UV-vis and fluorescence measurements. Further testimony of the formation of Ru=N interfacial linkages was highlighted in the unique reactivity of the nanoparticles with alkenes by imido transfer.
Extensive conjugation between metal-ligand interfacial bond results in remarkable intraparticle charge delocalization on Ru-alkynide nanoparticles, which was manipulated by simple chemical reduction or oxidation. Charging of extra electrons into the nanoparticle cores led to an electron-rich metal core and hence red-shift of the triple bond stretching mode, lower binding energy of sp hybridized C 1s and dimmed fluorescence of nanoparticles. Instead, chemical oxidation resulted in the opposite impacts on these properties.
By taking advantage of such extensively conjugated metal-ligand bonding and effective intraparticle charge delocalization of ruthenium nanoparticles, Ru=carbene nanoparticles functionalized with multiple moieties by olefin metathesis reactions was further exploited for metal ion sensing. When the nanoparticles were co-functionalized with 1-vinylpyrene and 4-vinylbenzo-18-crown-6, upon the binding of metal ions into the crown ether cavity, the emission intensity of the nanoparticle fluorescence from the conjugation of vinylpyrene was found to diminish, with the most significant effects observed with K+ ions. In the case of ruthenium nanoparticles co-functionalized with pyrene and histidine derivative moieties through Ru=carbene &pi bonds. The selective complexation of the histidine moiety with transition metal ions led to marked diminishment of the emission intensity from conjugation of pyrene. Of all the metal ions tested, the impacts were much more drastic with Pb2+, Co2+ and Hg2+ than with Li+, K+, Rb+, Mg2+ Ca2+ and Zn2+ ions.These were ascribed to the selective binding of 18-crown-6 to potassium ions or complexation of histidine derivative to transition metal ions, where the metal ions led to polarization of the nanoparticle core electrons to the metal surface and hence impeded intraparticle charge delocalization.
Functionalization of semiconductor with metal nanoparticles could be exploited to remarkably enhance their photo catalytic performance. Before this exploration, in the last chapter, the impacts of the TiO2 nanocrystalline structure on the photocatalytic activity were then examined by using the reduction of methylene blue in water. It was found that in the presence of anatase and brookite crystalline phase, TiO2 nanotube arrays exhibited the highest photo catalytic activity. This is ascribed to synergistic coupling of the anatase and brookite crystalline domains, which led to effective charge separation upon photoirradiation.