Rational design and facile hydrothermal-thermal conversion synthesis of hierarchical porous urchin-like Cu2−xSi2O5(OH)3·xH2O and CuO/SiO2 hollow microspheres for high efficiency catalytic reduction of nitroarenes and adsorption of organic dye

Abstract

Hierarchical porous urchin-like Cu2−xSi2O5(OH)3·xH2O hollow microspheres constructed by radially aligned one-dimensional (1D) nanotubes (NTs) are rationally designed and facilely fabricated via a one-pot hydrothermal method (120 °C, 12.0 h) using abundant CuCl2·2H2O and Na2SiO3·9H2O as the basic raw materials, in the absence of any pre-prepared templates, additives or organic solvents. A probable etching formation mechanism of the Cu2−xSi2O5(OH)3·xH2O hollow microspheres assisted by the intermediate SiO2 nanospheres is proposed. The subsequent mild thermal conversion (750 °C, 2.0 h) results in CuO/SiO2 composite hollow microspheres. Both of the hierarchical porous Cu2−xSi2O5(OH)3·xH2O and CuO/SiO2 composite microspheres present highly catalytic activity to the reduction of the nitroarenes (e.g. 4-NP and 2-NP). Particularly, the hierarchical porous Cu2−xSi2O5(OH)3·xH2O hollow microspheres bearing high specific surface area (528.2 m2 g−1) and large pore volume (1.083 cm3 g−1) and in situ reduced highly dispersed metallic Cu0 demonstrate high activity for the 4-NP reduction, with an exceptional rate constant (Knor = 60.6 s−1 g−1) higher than that of many other previously reported results. The synergic effect of the in situ reduced Cu0 and hierarchical porous structures on the reduction of 4-NP has also been deliberately investigated. Moreover, the Cu2−xSi2O5(OH)3·xH2O and CuO/SiO2 composite microspheres have also displayed excellent recycling catalytic performance during the tested 10 successive runs of reduction of 4-NP without significant degradation in its activity. Additionally, the Cu2−xSi2O5(OH)3·xH2O microspheres also exhibit excellent adsorption performance for removal of cationic dye methylene blue (MeB), with the maximum adsorption capacity qm of 242.5 mg g−1. The hierarchical porous Cu2−xSi2O5(OH)3·xH2O and CuO/SiO2 composite microspheres thus demonstrate great potentials as low-cost, environmentally friendly and competitive candidates in future practical wastewater treatment.