Hybrid biopolymer/metal–organic framework 3D-sponges towards the capture of the 'big five' heavy metals

most prevalent heavy metals: Hg(II), Pb(II), Cd(II), As(III/V), and Cr(VI). Traditional sorbents are limited in theirability to capture all the “big five” heavy metals, since they occur as cationic, neutral, or anionic species understandard conditions. To address this challenge, we have integrated a thiol rich Zr(IV)- Metal-Organic Framework (MOF), namely BCM-1, into a soy protein (SPI) and chitin (CHI) sponge in order to engineer a 3D-hybrid water filter. The components and the composite systems were thoroughly characterised by conventional means.Additionally, neutron imaging was used to reveal the 3D-interconnected micro- to macroporous structure of the filters, while Small-Angle X-ray Scattering (SAXS) confirmed the presence of BCM-1 as monodisperse nanoparticles. The 3D-sponge combines mechanical stability, high permeability, and broad chemical affinity, allowing the efficient removal of all five heavy metals through simple adjustments of its activation conditions. Adsorption experiments demonstrated over 90 % removal for most target metals depending if the hybrid-sponge is employed as synthesised, or after activating at pH = 1. When tested with 1 ppm solutions, they exhibit adsorption efficiencies for Hg(II), Pb(II), Cd(II), As(V), and Cr(VI) of 60.8/100 %, 94.4/74.8 %, 15.7/69.1 %, 100/38.2 %, 5.7/100 %, and 13.5/97.4 %, before and after the activation of the 3D-sponge, respectively. The metrics are consistently maintained over three adsorption/desorption cycles in surface water samples. On the whole, this work provides a scalable and sustainable approach to combine biopolymers and MOFs for real-world water remediation applications and highlights the key role of their protonation state on their absorptive properties.