Next, we investigated the influence of node identity on the high-and low-ratio gas adsorption preferences. There are distinct trends among different nodes, with some nodes exhibiting a preference for CO2 (e.g., nodes N38 and N61) while others favor CH4 (e.g., nodes particularly suitable for adsorbing CO2 over CH4. In addition to the aforementioned Co-based porphyrinic N41, N79 is also a CH4-favoring node. N79 is a Li4(OR)4 (R = pyridine) cubane cluster. This large node contains eight pyridines, resulting in a high void volume conducive to CH4 adsorption. These nodes do not exhibit open metal sites, explaining their relatively low CO2 adsorption. Of the four highlighted nodes, N41 and N61 have the greatest apparent influence on gas uptake preference. For 96% of N61-containing MOFs (65 out of 68), the CO2:CH4 ratio is greater than 1.1, while 88% of N41-containing MOFs (135 out of 153) have a ratio less than 0.9 (Supporting Information Figure ). This observation is consistent with earlier analysis where these nodes appeared frequently in the top 20 MOFs ranked by working capacity of CH4 and CO2, respectively.