Green synthesis of graphene oxide (GO)-anchored Pd/Cu bimetallic nanoparticles using Ocimum sanctum as bio-reductant: an efficient heterogeneous catalyst for the Sonogashira cross-coupling reaction

利用圣罗勒(Ocimum sanctum)作为生物还原剂,绿色合成氧化石墨烯(GO)锚定的Pd/Cu双金属纳米粒子:一种高效的Sonogashira交叉偶联反应非均相催化剂

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Abstract

To explore the synergism between two metal centers we have synthesized graphene oxide (GO) supported Pd/Cu@GO, Pd@GO and Cu@GO nanoparticles through bio-reduction of Pd(NO(3))(2) and CuSO(4)·5H(2)O using Tulsi (Ocimum sanctum) leaf extract as the reducing and stabilizing agent. The graphene oxide (GO) was obtained by oxidation of graphite following a simplified Hummer's method. The as-prepared nanomaterials have been extensively characterized by FTIR, powder X-ray diffraction (PXRD), HRTEM, TEM-EDS, XPS, ICP-AES and BET surface area measurement techniques. The morphological study of Pd/Cu@GO revealed that crystalline bimetallic alloy type particles were dispersed on the GO layer. The activity of Pd@GO, Cu@GO and Pd/Cu@GO as catalysts for the Sonogashira cross-coupling reaction have been investigated and it was found that the Pd/Cu@GO nanostructure showed highly superior catalytic activity over its monometallic counterparts, substantiating the cooperative influence of the two metals. The inter-atom Pd/Cu transmetalation between surfaces was thought to be responsible for its synergistic activity. The catalyst showed higher selectivity towards coupling of aryl iodides with both aliphatic and aryl alkynes resulting in moderate to excellent isolated yield of the desired products (45-99%). The products have been characterized by GC-MS and (1)H-NMR spectroscopic techniques and compared with authentic samples. The Pd/Cu@GO catalyst could be easily isolated from the reaction products and reused for up to at least ten successive runs effectively.

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