The Surface of Colloidal Metal-Organic Framework Nanoparticles Revealed by Vibrational Sum Frequency Scattering Spectroscopy.

Solvation shells strongly influence the interfacial chemistry of colloidal systems, from the activity of proteins to the colloidal stability and catalysis of nanoparticles. Despite their fundamental and practical importance, solvation shells have remained largely undetected by spectroscopy. Furthermore, their ability to assemble at complex but realistic interfaces with heterogeneous and rough surfaces remains an open question. Here, we apply vibrational sum frequency scattering spectroscopy (VSFSS), an interface-specific technique, to colloidal nanocrystals with porous metal-organic frameworks (MOFs) as a case study. Due to the porous nature of the solvent-particle boundary, MOF particles challenge conventional models of colloidal and interfacial chemistry. Their multiweek colloidal stability in the absence of conventional surface ligands suggests that stability may arise in part from solvation forces. Spectra of colloidally stable Zn(2-methylimidazolate) 2 (ZIF-8) in polar solvents indicate the presence of ordered solvation shells, solvent-metal binding, and spontaneous ordering of organic bridging linkers within the MOF. These findings help explain the unexpected colloidal stability of MOF colloids, while providing a roadmap for applying VSFSS to wide-ranging colloidal nanocrystals in general.