Baldovi Herme G, Valencia Susana, Alvaro Mercedes, Asiri Abdullah M, Garcia Hermenegildo
Instituto Universitario de Tecnologia Quimica CSIC-UPV and Departamento de Química, Univ. Politecnica Valencia, Av. De los Naranjos S/N 46022, Valencia, Spain.
Nanoscale. 2015 Feb 7;7(5):1744-52. doi: 10.1039/c4nr05295a.
C-dots obtained in the homogeneous phase may exhibit a broad particle size distribution. The formation of C-dots within nanometric reaction cavities could be a methodology to gain control on their size distribution. Among the various possibilities, in the present work, the cavities of small pore size zeolites have been used to confine C-dots generated by the pyrolysis of the organic structure directing agent present in the synthesis of these crystalline aluminosilicates. To explore this methodology, ITQ-29 zeolite having a Linde type A (LTA) structure was prepared as pure silica with 4-methyl-2,3,6,7-tetrahydro-1H,5H-pyrido[3.2.1-ij]quinolinium as the organic structure directing agent. Pyrolysis under an inert atmosphere at 550 °C of a pure-silica ITQ-29 sample (cubic particles of 4 μm edge) renders a highly fluorescent zeolite containing about 15 wt% of the carbonised residue. While another small pore zeolite, ITQ-12 (ITW), also renders photoluminescent C-dots under similar conditions, medium or large pore zeolites, such as silicalite (MFI) or pure silica Beta (BEA), failed to produce fluorescent powders under analogous thermal treatment and only decomposition and complete removal of the corresponding quaternary ammonium ion templates was observed for these zeolites. The dissolution of the pyrolysed ITQ-29 zeolite framework and the extraction of the carbon residue with ethyl acetate have allowed the characterisation of C-dots with particle sizes between 5 and 12 nm and a photoluminescence quantum yield of 0.4 upon excitation at 350 nm that is among the highest reported for non-surface functionalized C-dots. Photoluminescence varies with the excitation wavelength and is quenched by oxygen. Pyrolysed ITQ-29 powders can act as fluorescent oxygen sensors.
在均相中获得的碳点可能呈现出较宽的粒径分布。在纳米反应腔体内形成碳点可能是一种控制其粒径分布的方法。在各种可能性中,在本工作中,小孔径沸石的腔体已被用于限制由这些结晶铝硅酸盐合成中存在的有机结构导向剂热解产生的碳点。为了探索这种方法,制备了具有A型(LTA)结构的ITQ-29沸石,其为纯二氧化硅,使用4-甲基-2,3,6,7-四氢-1H,5H-吡啶并[3.2.1-ij]喹啉鎓作为有机结构导向剂。在550℃的惰性气氛下对纯二氧化硅ITQ-29样品(边长为4μm的立方颗粒)进行热解,得到一种高度荧光的沸石,其含有约15 wt%的碳化残渣。虽然另一种小孔径沸石ITQ-12(ITW)在类似条件下也能产生光致发光的碳点,但中孔或大孔径沸石,如硅沸石(MFI)或纯二氧化硅β沸石(BEA),在类似的热处理下未能产生荧光粉末,并且仅观察到这些沸石中相应季铵离子模板的分解和完全去除。热解后的ITQ-29沸石骨架的溶解以及用乙酸乙酯萃取碳残渣,使得能够表征粒径在5至12nm之间且在350nm激发时光致发光量子产率为0.4的碳点,这是未进行表面功能化的碳点中报道的最高值之一。光致发光随激发波长而变化,并被氧气猝灭。热解后的ITQ-29粉末可作为荧光氧传感器。