Dipartimento Scienze e Tecnologie Biologiche, Chimiche e Farmaceutiche (STEBICEF) Università degli Studi di Palermo , Viale delle Scienze, Ed. 17, 90128 Palermo, Italy.
Istituto per lo Studio dei Materiali Nanostrutturati ISMN-CNR , Via Ugo La Malfa 153, 90146 Palermo, Italy.
ACS Nano. 2016 Apr 26;10(4):4627-36. doi: 10.1021/acsnano.6b00936. Epub 2016 Mar 28.
We report the synthesis and catalytic properties of single-walled carbon nanotube-polyamidoamine dendrimers hybrids (SWCNT-PAMAM), prepared via a convergent strategy. The direct reaction of cystamine-based PAMAM dendrimers (generations 2.5 and 3.0) with pristine SWCNTs in refluxing toluene, followed by immobilization and reduction of PdCl4, led to the formation of highly dispersed small palladium nanoparticles homogeneously confined throughout the nanotube length. One of these functional materials proved to be an efficient catalyst in Suzuki and Heck reactions, able to promote the above processes down to 0.002 mol % showing a turnover number (TON) of 48 000 and a turnover frequency (TOF) of 566 000 h(-1). In addition, the hybrid material could be recovered and recycled for up to 6 times. No leaching of the metal has been detected during the Suzuki coupling. Additional experiments carried out on the spent catalyst permitted to suggest that a "release and catch" mechanism is operative in both reactions, although during Heck reaction small catalytically active soluble Pd species are also present.
我们报告了通过收敛策略制备的单壁碳纳米管-聚酰胺胺树枝状聚合物杂化物(SWCNT-PAMAM)的合成和催化性能。在回流甲苯中,通过半胱氨酸基 PAMAM 树枝状大分子(第 2.5 和 3.0 代)与原始 SWCNT 的直接反应,随后固定和还原[PdCl4](2-),导致高度分散的小钯纳米颗粒均匀地限制在纳米管长度内。其中一种功能材料被证明是Suzuki 和 Heck 反应中的有效催化剂,能够在 0.002 mol%的低用量下促进上述过程,其周转数(TON)为 48000,转化频率(TOF)为 566000 h-1。此外,该混合材料可以回收并重复使用多达 6 次。在 Suzuki 偶联过程中没有检测到金属浸出。在用过的催化剂上进行的附加实验表明,在这两种反应中都存在“释放和捕获”机制,尽管在 Heck 反应中也存在少量具有催化活性的可溶性 Pd 物种。