Abstract

The abundance of Cu-contaminated effluents and the serious risk of contamination of the aquatic systems combine to provide strong motivating factors to tackle this environmental problem. The treatment of polluted effluents by rhizofiltration and biosorption is an interesting ecological alternative. Taking advantage of the remarkable ability of the selected plants to bioconcentrate copper into roots, these methods have been exploited for the decontamination of copperrich effluents. Herein, we present an overview on the utility of the resulted copper-rich biomass for the preparation of novel bio-sourced copper-based catalysts for copper-mediated reactions: from the bioaccumulation of copper in plant, to the preparation and full analysis of the new Eco-Cu catalysts, and their application in selected key reactions. The hydrolysis of a thiophosphate, an Ullmanntype coupling leading to N- and O-arylated compounds, and a CuAAC “click” reaction, all performed under green and environmentally friendly conditions, will be described.

Highlights

  • Numerous of the greatest successes of organometallic and inorganic chemistry are based on the use of metal complexes for catalysis and organic synthesis [1,2]

  • We will focus on the rhizofiltration and biosorption that have been used by Grison et al to prepare copper ecocatalysts [69,70,71]

  • The first examples of Cu catalysts of plant origin, Eco-Cu, were presented in this review. These catalysts resulted from the bioaccumulation of copper by living or dead aquatic plants

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Summary

Introduction

Numerous of the greatest successes of organometallic and inorganic chemistry are based on the use of metal complexes for catalysis and organic synthesis [1,2]. MOF [49], efficiently reconcile copper-catalysis forimmobilized organic synthesis with theCuI protection of the on environment, alumina-supported CuO [50], and recent mesoporous copper supported on manganese oxide material (meso Cu/MnOx) [51] as well as copper oxide catalysts supported on three dimensional mesoporous aluminosilicates [52] are certainly worth mentioning. Given the importance of copper-based catalysis, the purpose of this review is to discuss the recent advances in the preparation of the first fully bio-based, ecological copper catalysts, named Eco-Cu, and their application in organic synthesis. This part highlights the possibility and feasibility to efficiently reconcile copper-catalysis for organic synthesis with the protection of the environment, including the preservation or remediation of aquatic systems. The synthetic potential of Eco-Cu will be illustrated through three major applications of copper catalysis: (i) the hydrolysis of the thiophosphate group in an important example of parathion [68], (ii) the Ullmann coupling for N- and O-arylation [69], and (iii) the CuAAC “click” reaction performed under green and environmentally friendly conditions [70]

Phytoaccumulation of Copper
Preparation via Rhizofiltration
Preparation by Biosorption
Identification of the Degree of Oxidation
Direct-Injection Mass Spectrometric Analysis of Eco-Cu3
Morphology Study of Eco-Cu3 by BET Analyses
XRD Analysis of the Eco-Cu3 Catalyst
Lewis and Brønsted Acidic Character
Cu-Catalysed Hydrolysis of Thiophosphates
Copper-Catalysed Ullmann Coupling Reactions
N-Arylation
Reaction 4 conditions
Reaction conditions:
O-Arylation Ullmann-type Reaction
The yields were
Application of Eco-Cu in the CuAAC Reaction
O i-PrOH
Reaction i-PrOH
A CuAAC substrate scope ofled the
11. A scope the Eco-Cu-catalysed is1323the activity ofofsubstrate the
Recycling and Reuse of the Ecocatalysts
The catalytic activity of the Eco-Cu recycled
Findings
Conclusions
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