Amine-rich cyclotriphosphazene (P3N3) nano-cages for enhanced and selective Au(III) and Pd(II) recovery and hydrogen generation: Waste-to-resource tactics

Abstract

Designing a new material for precious metals (PMs) recovery is of ultimate significance in the quest to explore highly efficient, selective, and stable adsorbents for a sustainable economy and green environment. Herein, novel amine-rich cyclotriphosphazene poly(tetrakis(4-aminophenyl)methane-co-cylotriphosphazene)- porous nano-cages (PTC-PNC) and microspheres (PTC-MS) were synthesized for adsorption and selective recovery of Au(III) and Pd(II) in aqueous solution. A combination of the abundant amine groups and the cage-like porous morphology of PTC-PNC makes it an ideal absorbent for recovery of the Au(III) (1592 mg g−1, pH 1.0, 60 oC) and Pd(II) (1372 mg g−1, pH 1.0, 60 oC) with high selectivity which was slightly decreased up to 8-11% even in the presence of 13 co-existing metals ions while an ultra-high recovery of 99% was obtained. The unique cage-like morphology of the PTC-PNC guarantees a fast adsorption equilibrium while the adsorption isotherm specifies a pseudo-second-order kinetic behavior and Langmuir isotherm. Amine groups were the most energetically favorable sites for the capturing and chelating of Au(III) and Pd(II) ions followed by their partial reduction to Au0 and Pd0. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron spectroscopy (HRTEM) analysis were employed to explore interactions and reduction mechanisms during the adsorption process. Adopting the waste-to-resource approach, after Au(III) and Pd(II) recovery, these adsorbents were applied for catalytic hydrogen generation from ammonia borane (AB) hydrolysis. Due to its favorable electronic structure, the PTC-PNC@Pd exhibited a higher hydrogen generation than PTC-PNC@Au. The as-synthesized PTC-PNC could be employed as a promising material for other MPs' selective recovery and green energy generation applications.