A post-synthetic modification strategy for enhancing Pt adsorption efficiency in MOF/polymer composites

Abstract

Growing polymers inside porous metal–organic frameworks (MOFs) can allow incoming guests to access the backbone of otherwise non-porous polymers, boosting the number and/or strength of available adsorption sites inside the porous support. In the present work, we have devised a novel post-synthetic modification (PSM) strategy that allows one to graft metal-chelating functionality onto a polymer backbone while inside MOF pores, enhancing the material's ability to recover Pt(IV) from complex liquids. For this, polydopamine (PDA) was first grown inside of a MOF, known as Fe-BTC (or MIL-100 Fe). Next, a small thiol-containing molecule, 2,3-dimercapto-1-propanol (DIP), was grafted to the PDA via a Michael addition. After the modification of the PDA, the Pt adsorption capacity and selectivity were greatly enhanced, particularly in the low concentration regime, due to the high affinity of the thiols towards Pt. Moreover, the modified composite was found to be highly selective for precious metals (Pt, Pd, and Au) over common base metals found in electronic waste (i.e., Pb, Cu, Ni, and Zn). X-ray photoelectron spectroscopy (XPS) and in situ X-ray absorption spectroscopy (XAS) provided insight into the Pt adsorption/reduction process. Last, the PSM was extended to various thiols to demonstrate the versatility of the chemistry. It is hoped that this work will open pathways for the future design of novel adsorbents that are fine-tuned for the rapid, selective retrieval of high-value and/or critical metals from complex liquids.