Chen Mengjun, Zhang Geping, Jiang Yue, Yin Keyang, Zhang Linwen, Li Hongguang, Hao Jingcheng
Key Laboratory of Colloid and Interface Chemistry & Key Laboratory of Special Aggregated Materials , Shandong University, Ministry of Education , Jinan 250100 , China.
State Key Laboratory of Solid Lubrication , Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences , Lanzhou 730000 , China.
Langmuir. 2019 Jul 2;35(26):8806-8815. doi: 10.1021/acs.langmuir.9b00193. Epub 2019 Jun 18.
Biomineralization is a typical methodology developed by nature to produce calcium-based materials. A method mimicking this process has nowadays become popular for the preparation of artificial organic-inorganic hybrids. Here, Cu(PO) crystals with a flowerlike morphology have been prepared using water-soluble derivatives of fullerene C as templates. In a typical system, flowerlike crystals of Cu(PO) (denoted FLCs-Cu) were obtained by simply dropping an aqueous solution of CuSO into phosphate-buffered saline (PBS) containing a highly water-soluble multiadduct of C (fullerenol). The best condition for the preparation of FLCs-Cu appeared at 0.20 mg·mL fullerenol and 0.10 mol·L PBS. During the formation of FLCs-Cu, fullerenol acts as a template and its content in FLCs-Cu is trace (less than 5% by atom) as confirmed by scanning electron microscopy mapping and thermogravimetric analysis. This feature makes fullerenol reusable, and the FLCs-Cu can be prepared repeatedly using the same fullerenol aqueous solution at least 10 times without a noticeable change in the morphology. The N adsorption/desorption isotherm showed that the doping of fullerenol increased the specific surface area of the Cu(PO) crystal. When fullerenol was replaced by C monoadducts that are cofunctionalized with a pyrrolidine cation and oligo(poly(ethylene oxide)) chains, FLCs-Cu can form as well, indicating that the strategy of using water-soluble C derivative as a template to get FLCs-Cu is universal. As a typical example of practical applications, the photocatalytic activity of the FLCs-Cu was investigated toward the degradation of dyes including rhodamine B and rhodamine 6G. In both cases, efficient photodegradation has been confirmed.
生物矿化是自然界发展出的一种用于生产钙基材料的典型方法。如今，一种模仿此过程的方法已广泛应用于制备人工有机-无机杂化材料。在此，已使用富勒烯C的水溶性衍生物作为模板制备出具有花状形态的Cu(PO)晶体。在一个典型体系中，通过将CuSO水溶液简单滴加到含有高水溶性C多加成物（富勒醇）的磷酸盐缓冲盐水（PBS）中，获得了Cu(PO)的花状晶体（记为FLCs-Cu）。制备FLCs-Cu的最佳条件出现在富勒醇浓度为0.20 mg·mL 且PBS浓度为0.10 mol·L时。在FLCs-Cu的形成过程中，富勒醇充当模板，并且通过扫描电子显微镜映射和热重分析证实其在FLCs-Cu中的含量极微（原子百分比小于5%）。这一特性使得富勒醇可重复使用，并且可以使用相同的富勒醇水溶液至少重复制备FLCs-Cu 10次，而形态无明显变化。N吸附/解吸等温线表明，富勒醇的掺杂增加了Cu(PO)晶体的比表面积。当用与吡咯烷阳离子和聚（环氧乙烷）链共官能化的C单加成物替代富勒醇时，也能形成FLCs-Cu，这表明使用水溶性C衍生物作为模板来制备FLCs-Cu的策略具有通用性。作为实际应用的一个典型例子，研究了FLCs-Cu对包括罗丹明B和罗丹明6G在内的染料降解的光催化活性。在这两种情况下，均已证实有高效的光降解作用。
