Highly efficient and acid-resistant metal-organic frameworks of MIL-101(Cr)-NH₂ for Pd(II) and Pt(IV) recovery from acidic solutions: Adsorption experiments, spectroscopic analyses, and theoretical computations

Cr-based metal-organic frameworks (MOFs) of MIL-101(Cr)-NH₂ was post-synthesized from nitro-functionalized MIL-101(Cr) (MIL-101(Cr)-NO₂) through a reduction process. Adsorption behaviors and interactions of MIL-101(Cr)-NH₂ and MIL-101(Cr)-NO₂ with platinum group metal (PGM) anions of Pd(II) (PdCl₄²⁻) and Pt(IV) (PtCl₆²⁻), were investigated through batch adsorption experiments, spectroscopic analyses, and theoretical computations. According to adsorption kinetics and isotherms, the uptakes of Pd(II) and Pt(IV) by in MIL-101(Cr)-NH₂ were found to be much higher than their uptakes by MIL-101(Cr)-NO₂. The abundant protonated amine groups (BDC-NH₃⁺) in MIL-101(Cr)-NH₂ were verified to be the main adsorptive binding sites by XPS and FTIR spectroscopy, and FE-SEM imageries. Additionally, BDC-NH₃⁺ shows extremely high affinities (b value) and binding energies (E_bind) for PdCl₄²⁻ and PtCl₆²⁻ through electrostatic attraction, resulting in much higher adsorption capacities of MIL-101(Cr)-NH₂ for these PGMs as compared to those of MIL-101(Cr)-NO₂. Moreover, the MOFs’ Cr nodes without terminal −OH indicated positive electrostatic potentials, and certain values of E_bind for PGM anions. Thus, the few-amount cationic Cr sites could also make little contributions to the adsorption of PGM anions in MIL-101(Cr)-NH₂ or MIL-101(Cr)-NO₂. Furthermore, the perfect regeneration and reusability of MIL-101(Cr)-NH₂ over five of adsorption-desorption cycles, suggesting its potential in practical applications.