Separating hydrocarbons from refinery dry gas is a fundamental demand in petrochemical industry. Metal-Organic Frameworks are a class of promising advanced adsorbents, yet better moisture stability and higher adsorptive selectivity are still needed to meet the requirement of petrochemical industry. Herein, a multifunctional adsorbent urea@Cu-BTC was prepared from cheap building blocks at room temperature, which exhibits generally enhanced adsorptive separation performance towards CO2/CH4, CO2/N2, C3H6/C3H8, C2H4/C2H6, CH4/N2 separation. More interestingly, urea@Cu-BTC shows significantly enhanced stability against moisture. Combining structural characterization and molecular simulation, the improved adsorptive separation performance was ascribed to the enhanced confinement from the creation of ultra-micro porosity due to the presence of urea molecule in the microporous channel of Cu-BTC. The major components in refinery dry gas can be well separated using a column filled with urea@Cu-BTC, which demonstrates that micro-regulating the channel of MOFs is a feasible strategy for preparing high performance petrochemical adsorbents.

We introduce a straightforward method for the preparation of novel starch-based ultramicroporous carbons (SCs) that demonstrate high CH4 uptake and excellent CH4/N2 selectivity. These SCs are derived from a combination of starch and 1-6 wt. % of acrylic acid, and the resulting materials are amenable to surface cation exchangeability as demonstrated by the formation of highly dispersed K+ in carbon precursors. Following activation, these SCs contain ultramicropores with narrow pore-size distributions of <0.7 nm, leading to porous carbon-rich materials that exhibit CH4 uptake values as high as 1.86 mmol/g at 100 kPa and 298 K, the highest uptake value for CH4 to date, with the IAST-predicted CH4/N2 selectivity up to 5.7. Both the potential mechanism for the formation of narrow pores and the origin of the favorable CH4 adsorption properties are discussed and examined. This work may potentially guide future designs for carbon-rich materials with excellent gas adsorption properties.