pH‐Regulated Refinement of Pore Size in Carbon Spheres for Size‐Sieving of Gaseous C₈, C₆ and C₃ Hydrocarbon Pairs

Selective separation of industrial important C 8 , C 6 and C 3 hydrocarbon pairs by physisorbents can greatly reduce the energy intensity related to the currently used cryogenic distillation techniques. The achievement of size‐sieving based on carbonaceous materials is desirable, but commonly hindered by the random structure of carbons often with a broad pore size distribution. Herein, a pH‐regulated pre‐condensation strategy was introduced to control the carbon pore architecture by the sp 2 /sp 3 hybridization of precursor. The lower pH value during pre‐condensation of glucose facilitates the growth of aromatic nanodomains, rearrangement of stacked layers and a concomitant transition from sp 3 ‐C to sp 2 ‐C. The subsequent pyrolysis endows the pore size manipulated from 6.8 to 4.8 Å and narrowly distributed over a range of 0.2 Å. The refined pores enable effective size‐sieving of C 8 , C 6 and C 3 hydrocarbon pairs with high separation factor of 1.9 and 4.9 for C 8 xylene (X) isomers para ‐X/ meta ‐X and para ‐X/ ortho ‐X, respectively, 5.1 for C 6 alkane isomers n‐hexane/3‐methylpentane, and 22.0 for C 3 H 6 /C 3 H 8 . The excellent separation performance based‐on size exclusion effect is validated by static adsorption isotherms and dynamic breakthrough experiments. This synthesis strategy provides a means of exploring advanced carbonaceous materials with controlled hybridized structure and pore sizes for challenging separation needs.