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<p>The separation of ethane/ethylene is a key step in the petrochemical industry, yet it is extremely challenging because of their nearly identical physicochemical properties. Adsorptive separation based on porous materials, especially those that can selectively adsorb ethane (C<sub>2</sub>H<sub>6</sub>), can directly deliver polymer-grade ethylene (C<sub>2</sub>H<sub>4</sub>) in a single step, but this approach suffers from low efficiency because the more polarizable C<sub>2</sub>H<sub>4</sub> can also bind strongly. Herein, we report two isoreticular cluster-based hydrogen-bonded organic frameworks (HOFs), AS-HOF-2 and AS-HOF-3, for elevating the separation of C<sub>2</sub>H<sub>6</sub> from C<sub>2</sub>H<sub>4</sub>. The methyl incorporated AS-HOF-3 shows relatively compact pore aperture (4.35 Å vs. 4.56 Å in AS-HOF-2), resulting elevated C<sub>2</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> selectivity (AS-HOF-2a: 1.58, AS-HOF-3a: 1.66). Both HOFs can produce polymer-grade (&gt;99.95%) C<sub>2</sub>H<sub>4</sub> in one separation step, as demonstrated by breakthrough experiments. In particular, ease of high crystallinity enables both HOFs for direct visualization of host-guest interactions by their gas-loaded single-crystal structures. In addition, both HOFs exhibit exceptional chemical stability.</p>

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Isoreticular cluster-based hydrogen-bonded organic frameworks with optimized pore space for efficient C2H6/C2H4 separation

  • 期刊论文

  • 发表日期：

    2026年5月26日

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  • Xian-Xian Xiao,
  • Yu Wang,
  • Chao-Qun Dong,
  • Zi-Luo Fang,
  • Ding-Yi Hu,
  • Kai Zheng,
  • Jun-Xian Chen,
  • Rui-Biao Lin

摘要

The separation of ethane/ethylene is a key step in the petrochemical industry, yet it is extremely challenging because of their nearly identical physicochemical properties. Adsorptive separation based on porous materials, especially those that can selectively adsorb ethane (C2H6), can directly deliver polymer-grade ethylene (C2H4) in a single step, but this approach suffers from low efficiency because the more polarizable C2H4 can also bind strongly. Herein, we report two isoreticular cluster-based hydrogen-bonded organic frameworks (HOFs), AS-HOF-2 and AS-HOF-3, for elevating the separation of C2H6 from C2H4. The methyl incorporated AS-HOF-3 shows relatively compact pore aperture (4.35 Å vs. 4.56 Å in AS-HOF-2), resulting elevated C2H6/C2H4 selectivity (AS-HOF-2a: 1.58, AS-HOF-3a: 1.66). Both HOFs can produce polymer-grade (>99.95%) C2H4 in one separation step, as demonstrated by breakthrough experiments. In particular, ease of high crystallinity enables both HOFs for direct visualization of host-guest interactions by their gas-loaded single-crystal structures. In addition, both HOFs exhibit exceptional chemical stability.