Probing sub-5 Ångstrom micropores in carbon for precise light olefin/paraffin separation.

Du, Shengjun; Huang, Jiawu; Ryder, Matthew R; Daemen, Luke L; Yang, Cuiting; Zhang, Hongjun; Yin, Panchao; Lai, Yuyan et al. · Nat Commun · 2023

basic_science · Level V

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Abstract

Olefin/paraffin separation is an important but challenging and energy-intensive process in petrochemical industry. The realization of carbons with size-exclusion capability is highly desirable but rarely reported. Herein, we report polydopamine-derived carbons (PDA-Cx, where x refers to the pyrolysis temperature) with tailorable sub-5 Å micropore orifices together with larger microvoids by one-step pyrolysis. The sub-5 Å micropore orifices centered at 4.1-4.3 Å in PDA-C800 and 3.7-4.0 Å in PDA-C900 allow the entry of olefins while entirely excluding their paraffin counterparts, performing a precise cut-off to discriminate olefin/paraffin with sub-angstrom discrepancy. The larger voids enable high C<sub>2</sub>H<sub>4</sub> and C<sub>3</sub>H<sub>6</sub> capacities of 2.25 and 1.98 mmol g<sup>-1</sup> under ambient conditions, respectively. Breakthrough experiments confirm that a one-step adsorption-desorption process can obtain high-purity olefins. Inelastic neutron scattering further reveals the host-guest interaction of adsorbed C<sub>2</sub>H<sub>4</sub> and C<sub>3</sub>H<sub>6</sub> molecules in PDA-Cx. This study opens an avenue to exploit the sub-5 Å micropores in carbon and their desirable size-exclusion effect.