Meza-Laguna V, Basiuk E V, Alvarez-Zauco E, Acosta-Najarro D, Basiuk V A
Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autdnoma de México, Circuito Exterior, Ciudad Universitaria, 04510 México, DF Mexico.
J Nanosci Nanotechnol. 2007 Oct;7(10):3563-71. doi: 10.1166/jnn.2007.681.
We applied the direct solvent-free functionalization of fullerene C60 with aliphatic bifunctional amine, 1,8-diaminooctane, to prepare chemically cross-linked C60 thin films capable of binding silver nanoparticles. The gas-phase diamine treatment of C60 reduced dramatically the fullerene solubility in toluene, indicating the transformation of pristine C60 into a different solid phase with cross-linked fullerene molecules. Compared to the spectra of pristine C60 film and powder samples, Fourier-transform infrared, UV-Visible, Raman, and 13C nucleic magnetic resonance spectra of the functionalization products exhibited new features, which point to a breaking of C60 ideal structure during the formation of new covalent bonds and to the appearance of sp3 hibridization. The covalent functionalization with 1,8-diaminooctane allowed for a stable and homogeneous deposition of silver nanoparticles of ca. 5-nm diameter onto the functionalized films through the coordination bonding between metal atoms and nitrogen donor atoms of the fullerene derivatives. The proposed mechanism of Ag nanoparticle binding was supported by density functional theory calculations using the hybrid BLYP functional in conjunction with the double numerical basis set DND.
我们采用脂肪族双官能胺1,8 - 二氨基辛烷对富勒烯C60进行直接无溶剂功能化处理，以制备能够结合银纳米颗粒的化学交联C60薄膜。对C60进行气相二胺处理后，富勒烯在甲苯中的溶解度大幅降低，这表明原始的C60已转变为具有交联富勒烯分子的不同固相。与原始C60薄膜和粉末样品的光谱相比，功能化产物的傅里叶变换红外光谱、紫外可见光谱、拉曼光谱和13C核磁共振光谱呈现出新的特征，这表明在形成新的共价键过程中C60的理想结构被破坏，且出现了sp3杂化。通过1,8 - 二氨基辛烷进行共价功能化，使得直径约为5纳米的银纳米颗粒通过金属原子与富勒烯衍生物的氮供体原子之间的配位键，稳定且均匀地沉积在功能化薄膜上。使用杂化BLYP泛函结合双数值基组DND进行的密度泛函理论计算支持了所提出的银纳米颗粒结合机制。
