Single-Step Synthesized Functionalized Copper Carboxylate Framework Meshes as Hierarchical Catalysts for Enhanced Reduction of Nitrogen-Containing Phenolic Contaminants

Abstract

Nitrogen-containing phenolic contaminants (NCPCs) represent typical pollutants of industrial wastewaters. As catalytic reduction of NCPCs is a useful technique and Cu is an efficient metal catalyst, Cu-carboxylate frameworks (CuCF) are favorable materials. However, they are in powder form, making them difficult to use; thus, in this study, CuCF was grown on macroscale supports. Herein, we present a facile approach to develop such a CuCF composite by directly using a Cu mesh to grow CuCF on the mesh through a single-step electrochemical synthesis method, forming CuCF mesh (CFM). CFM could be further modified to afford CuCF mesh with amines (NH2) (CFNM), and CuCF mesh with carboxylates (COOH) (CFCM). These CuCF meshes are compared to investigate how their physical and chemical characteristics influenced their catalytic behaviors for reduction/hydrogenation of NPCPs, including nitrophenols (NPs) and dyes. Their nanostructures and surface properties influence their behaviors in catalytic reactions. In particular, CFCM appears to be the most efficient mesh for catalyzing 4-NP, with a much higher rate constant. CFCM also shows a significantly lower Ea (28.1 kJ/mol). CFCM is employed for many consecutive cycles, as well as convenient filtration-type 4-NP reduction. These CuCF meshes can also be employed for decolorization of methylene blue and methyl orange dyes via catalytic hydrogenation.