Metal confined in metal‐organic framework‐based mixed matrix membranes for efficient butadiene recognition separation

Abstract

The efficient separation of butadiene (1,3‐C4H6) from C4 hydrocarbons is a critical step in petrochemical processes. However, the traditional cryogenic distillation suffers from energy‐intensity and serious environmental stress, necessitating the development of alternative technologies for efficient 1,3‐C4H6 separation. Herein, a 1,3‐C4H6 recognition mixed matrix membrane is reported via incorporating metal copper encapsulated a metal‐organic framework (CuBTC@Cu) into elastic poly(dimethylsiloxane) (PDMS). The resulting CuBTC@Cu/PDMS membrane can efficient separate 1,3‐C4H6 from various C4 hydrocarbons including 1,3‐C4H6/n‐C4H8, 1,3‐C4H6/iso‐C4H8, 1,3‐C4H6/n‐C4H10 and 1,3‐C4H6/iso‐C4H10, yielding superior selectivity of 5.11, 6.35, 4.78, and 10.30, respectively, with 1,3‐C4H6 permeability of 53240 Barrer. Notably, the appropriate π‐complexation interaction between butadiene molecules and CuBTC@Cu as well as suitable transmission channel size enable the membrane only permeable to 1,3‐C4H6 and block the permeation of other C4 hydrocarbons, showing a unique 1,3‐C4H6 recognition behavior in membrane separation. The concept of affinity‐relying separation combining molecular sieving would open a new direction for designing gas membranes for efficient light hydrocarbon separations.

Introducing Carborane Clusters into Crystalline Frameworks via Thiol‐Yne Click Chemistry for Energetic Materials

“…Nitrogen sorption experiments confirmed this, with CB−SH@Zn(VIm) 2 displaying diminished adsorption capacity and a reduced Brunauer−Emmett−Teller (BET) specific surface area from 988 to 356 m 2 g −1 (Figure 2b). Pore size distribution diagrams revealed a notable decrease in central pore size (Figure 2c), aligning well with CB−SH dimensions (7.8 Å), suggesting nearly complete pore occupation by CB−SH [43,44] . FT‐IR spectra showcased distinctive B−H and C−S peaks at 2587 cm −1 and 721 cm −1 , respectively, characteristic of the CB−SH moiety (Figure 2d).…”

Introducing Carborane Clusters into Crystalline Frameworks via Thiol‐Yne Click Chemistry for Energetic Materials

“…Pore size distribution diagrams revealed a notable decrease in central pore size (Figure 2c), aligning well with CBÀ SH dimensions (7.8 Å), suggesting nearly complete pore occupation by CBÀ SH. [43,44] FT-IR spectra showcased distinctive BÀ H and CÀ S peaks at 2587 cm À 1 and 721 cm À 1 , respectively, characteristic of the CBÀ SH moiety (Figure 2d). Energydispersive X-ray spectroscopy (EDS) element mapping further confirmed uniform distribution of B, C, N, S, and Zn elements within the structures, underscoring the homogeneous distribution of CBÀ SH into the framework substrates (Figure S9).…”