Zeolitic imidazolate frameworks (ZIFs) have been widely investigated for numerous applications including energy storage, heterogeneous catalysis, and greenhouse gas adsorption. Much of the early work has focused on the bulk properties of microcrystalline ZIFs. Herein, we focus on identifying the nature of the surface of ZIF-8 by studying a supported ZIF-8 nanoparticle film using surface characterization techniques. We have experimentally identified the presence of a zinc-rich surface terminated by carbonates and water/hydroxyl groups (in addition to the expected methylimidazole terminations) using X-ray photoelectron spectroscopy (XPS). The thermal stability of ZIF-8 thin films was also investigated using scanning electron microscopy (SEM) and temperature-programmed reaction spectroscopy (TPRS). We determined the onset of decomposition of ZIF-8 thin films to be approximately 630 K using TPRS in an ultrahigh vacuum (UHV) environment. This work presents the first characterization steps needed to study the evolution of ZIF surfaces in situ using surface characterization techniques. Such techniques are capable of determining reaction products and tracking intermediates and surface evolution in gas adsorption/reaction studies of thin films.

The adsorption of CO 2 and H 2 O by ZIF-8 thin films was investigated using X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) in situ under low-temperature, low-pressure conditions. Using these two techniques, we demonstrate the ability to clearly distinguish molecules that exhibit significant adsorption in the pore structure of ZIF-8, from molecules that adsorb predominantly at outer surface sites. In particular, CO 2 was found to penetrate into the pore structure, while H 2 O resided predominantly at the surface. CO 2 uptake was quantified, and mobility within the films was investigated. The ability to distinguish surface processes from those that primarily occur in the bulk is key to understanding the properties of nanoporous materials.