Prussian blue analogues (PBAs) are low-cost porous materials with promising potential in gas separation, owing to their abundance of open metal sites. To access these open metal sites PBAs need to be activated through removal of water from the porous structure. However, the conditions required for effective activation and their structural consequences remain poorly understood, with existing effective methods being costly. Therefore, to gain insights in the activation process and its effects on structure, we systematically investigated the effect of activation temperature on three different ferricyanide-based PBAs (FePBA, CoPBA, and CuPBA) using a simple nitrogen flow activation procedure. We successfully synthesised these structures and optimised the activation procedure for micropore capacity and crystallinity. Infrared spectroscopy as well as CO2 and CO adsorption measurements revealed that, even under optimised conditions, water remained within the PBAs, with only a limited number of open metal sites accessible. At higher activation temperatures, micropore capacity and crystallinity decrease. This hydrophilicity, however, also showed positives, for example in the application of PBAs as desiccants. CuPBA, specifically, boasts a water adsorption of 355 mg g􀀀 1 at a relative humidity of ≤10%, competitive with zeolites and silica per weight unit, but higher per volume unit. Overall, however, while PBAs offer promise for gas adsorption owing to their high surface area and low cost, practical utilisation of their open metal sites remains challenging due to their strong affinity for water.

A key challenge in capturing CO2 from postcombustion gases is humidity due to competitive adsorption between CO2 and H2O. Multivariate (MTV) metal-organic frameworks (MOFs) have been considered a promising option to address this problem, e.g., combining CO2-affinitive and hydrophobic groups. Here, we synthesized a series of amine and methyl cofunctionalized MTV MIL-53(Al)-xNH2(1 - x)CH3 and their parent materials. All the mixed linker MIL-53(Al)-xNH2(1 - x)CH3 showed amino linker enrichment compared to the synthesis ratio, yet the linkers were distributed relatively homogeneously from the bulk to the surface. Material hydrophobicity or hydrophilicity varied with methyl or amino group content, respectively. The single-component adsorption indicated that certain mixed linker MIL-53(Al)-xNH2(1 - x)CH3 might outcompete the parent materials. In CO2-H2O competitive adsorption, however, the hydrophobic parental MIL-53(Al)-CH3 outperformed the mixed linker MOFs. CO2 adsorption capacities of 5.4, 4.9, and 3.6 wt % were found for 0.3 bar of CO2 under 0, 5, and 10% RH, respectively. The results highlight that materials with enhanced hydrophobicity and tight-fitting pores can outperform groups with high CO2 affinity in the CO2 capture under humid conditions.

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.

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.