In a world where capture and separation processes represent above 10% of global energy consumption, novel porous materials, such as Metal-Organic Frameworks (MOFs) used in adsorption-based processes are a promising alternative to dethrone the high-energy-demanding distillation. Shape and size tailor-made pores in combination with Lewis acidic sites can enhance the adsorbate-adsorbent interactions. Understanding the underlying mechanisms of adsorption is essential to designing and optimizing capture and separation processes. Herein, we analyze the adsorption behaviour of light hydrocarbons (methane, ethane, ethylene, propane, and propylene) in two synthesized copper-based MOFs, Cu-MOF-74 and URJC-1. The experimental and computational adsorption curves reveal a limited effect of the exposed metal centers on the olefins. The lower interaction Cu-olefin is also reflected in the calculated enthalpy of adsorption and binding geometries. Moreover, the diamond-shaped pores' deformation upon external stimuli is first reported in URJC-1. This phenomenon is highlighted as the key to understanding the adsorbent's responsive mechanisms and potential in future industrial applications.

In order to capture and separate CO2 from the air or flue gas streams through nanoporous adsorbents, the influence of the humidity in these streams has to be taken into account as it hampers the capture process in two main ways: (1) water preferentially binds to CO2 adsorption sites and lowers the overall capacity, and (2) water causes hydrolytic degradation and pore collapse of the porous framework. Here, we have used a water-stable polyimide covalent organic framework (COF) in N2/CO2/H2O breakthrough studies and assessed its performance under varying levels of relative humidity (RH). We discovered that at limited relative humidity, the competitive binding of H2O over CO2 is replaced by cooperative adsorption. For some conditions, the CO2 capacity was significantly higher under humid versus dry conditions (e.g., a 25% capacity increase at 343 K and 10% RH). These results in combination with FT-IR studies on equilibrated COFs at controlled RH values allowed us to assign the effect of cooperative adsorption to CO2 being adsorbed on single-site adsorbed water. Additionally, once water cluster formation sets in, loss of CO2 capacity is inevitable. Finally, the polyimide COF used in this research retained performance after a total exposure time of >75 h and temperatures up to 403 K. This research provides insight in how cooperative CO2-H2O can be achieved and as such provides directions for the development of CO2 physisorbents that can function in humid streams.