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Copper-coordination polymers Controlled Cu@N-rGO or CuO@C Nanoparticles Formation: Reusable Green Catalyst for A-3 Coupling and Nitroarene Reduction

Abstract

The choice of metal ions and organic linkers together with intriguing structural assembly make coordination polymers (COPs) as potential precursors for fabricating carbon encapsulated metal and metal oxide nanoparticles (NPs). Herein, we have studied the role of COPss structural assembly that was prepared by subtle change in the ligand structure on the formation of NPs in the carbon matrix. Cu-COPs (Cu-COPs-1 - 7) generated using different amino acid based reduced Schiff base phenolic chelating ligands showed crystalline structure with different structural organization in the solid state. Interestingly, calcination of Cu-COP-1 and Cu-COP-5 at 330 C produced pure CuNPs whereas Cu-COP-2, 3, 4 and 7 gave CuONPs encapsulated by carbon matrix. The calcination of Cu-COP-6 produced both Cu and CuONPs together in the carbon matrix. The formation of Cu and CuONPs in the carbon matrices were unambiguously confirmed by PXRD and XPS studies. The size and morphologies of Cu/CuONPs were analyzed using HR-TEM and FE-SEM. BET studies revealed higher surface area with small pores for CuNPs encapsulated by carbon and lower surface area with higher porosity for CuO-carbon matrix. Raman spectra revealed the formation of nitrogen doped reduced graphene oxide (N-rGO) carbon matrix in CuNPs-1. The N-rGO coverage and high surface area with small pores provided CuNPs-1 good stability in strong acid (10 M H2SO4). Importantly, the fabricated N-rGO encapsulated CuNPs-1 and carbon covered CuONPs-4 nanocomposites have been used as green catalyst in solvent free neat A3-coupling and nitroarene reduction reactions, respectively. The products were confirmed by 1H-NMR spectra. The recovered CuNPs-1 and CuONPs-4 catalysts after the completion of reactions have also shown similar catalytic activity up to five cycles without significant lose of catalytic activity. Thus the present studies demonstrated the influence of Cu-COPs structural assembly on the formation of Cu/CuONPs as well as carbon matrix and open the possibility of fabricating functional nanomaterials from vast available COPs with intriguing structural motifs.

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Supplementary files

Publication details

The article was received on 10 Jun 2017, accepted on 26 Jul 2017 and first published on 26 Jul 2017


Article type: Paper
DOI: 10.1039/C7DT02119D
Citation: Dalton Trans., 2017, Accepted Manuscript
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    Copper-coordination polymers Controlled Cu@N-rGO or CuO@C Nanoparticles Formation: Reusable Green Catalyst for A-3 Coupling and Nitroarene Reduction

    V. Vinod Kumar, R. Rajamani, P. Vairaprakash, M. Mariappan and P. P. Anthony, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT02119D

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