Evaluation of Iron-Based Metal-Organic Framework Activation Temperatures in Acetylene Adsorption

One of the major issues regarding long-term human space exploration is the need for a breathable atmosphere. A major component toward achieving this goal is both the removal of exhaled carbon dioxide (CO₂) and the generation or recovery of oxygen (O₂). NASA's current technology only operates at about 50% efficiency due to the need to vent the methane that is produced during the CO₂ reduction process. One method of improving the efficiency of this process is through plasma pyrolysis, wherein the methane is pyrolyzed to produce hydrogen and various dehydrogenated carbon byproducts. In this process, acetylene is one of the main components of this byproduct stream. Unfortunately, while the concentration of this effluent is generally high in hydrogen (>90% typically), the presence of the acetylene waste product can act as a poison for the ruthenium-alumina catalyst used in the CO₂-reducing Sabatier process, requiring a removal step. Metal-organic frameworks (MOFs) represent a valuable method for removing these unsaturated hydrocarbons due to their high tunability, particularly through the incorporation of open metal sites. In this study, two common iron-based MOFs, MIL-100 and PCN-250, were studied for their ability to adsorb acetylene. A combination of gas adsorption analysis and density functional theory calculation results shows the ability of these materials to undergo a thermal-induced reduction event, which results in an improvement in gas adsorption performance. This improvement in gas performance appears to be at least partially due to the increased presence of π-backbonding toward the acetylene molecules.