Das Nitumani, Maibam Ashakiran, Yun Hongryeol, Boro Bishal, Hong Chang Seop, Babarao Ravichandar, Mondal John
Department of Catalysis & Fine Chemicals, CSIR-Indian Institute of Chemical Technology, Uppal Road, Hyderabad 500 007, India.
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India.
Inorg Chem. 2024 Oct 21;63(42):19759-19768. doi: 10.1021/acs.inorgchem.4c02987. Epub 2024 Oct 9.
The potential to produce high-purity CH has made ethylene-selective adsorbents for ethane (CH)/ethylene (CH) gas mixture separation appealing as viable substitutes for traditional cryogenic distillation. In this aspect, porous organic polymers (POPs) are anticipated to become the next-generation potential adsorbent due to their easily customizable functions and functional sites suitable for gas separation. This article reports the selective CH adsorption over CH using microporous copper(I)-coordinated POP () via fine-tuning of the π complexation and pore size. The specially designed adsorbent has the ideal pore size and coordinated Cu(I) ions to form π-complexation with CH molecules, which enabled it to adsorb CH (at 1 bar, 24.9, 18.9, and 13.4 cm g at 273, 298, and 323 K, respectively) while significantly reducing CH adsorption (at 1 bar, 16.9, 12.7, and 8.8 cm g at 273, 298, and 323 K, respectively). At 1 bar, exhibited IAST selectivities of 6.09, 5.60, and 4.13 for CH/CH at 273, 298, and 323 K, respectively, suggesting its CH selective behavior, which was further confirmed from the experimental breakthrough measurement. Furthermore, the computational studies carried out with density functional theory highlighted an enhanced charge distribution leading to dπ-pπ conjugation between CH π-electrons and Cu d-electrons, thereby showing a relatively higher interaction energy of -37.23 kcal/mol with CH as compared to -16.06 kcal/mol with CH gas molecules.
生产高纯度乙烷（C₂H₆）的潜力使得用于乙烷（C₂H₆）/乙烯（C₂H₄）气体混合物分离的乙烯选择性吸附剂成为传统低温蒸馏可行的替代方案，具有吸引力。在这方面，多孔有机聚合物（POPs）因其易于定制的功能和适用于气体分离的功能位点，有望成为下一代潜在吸附剂。本文报道了通过微调π络合和孔径，使用微孔铜（I）配位的POP（）对C₂H₄进行C₂H₆选择性吸附。这种特殊设计的吸附剂具有理想的孔径和配位的Cu（I）离子，可与C₂H₆分子形成π络合，使其能够吸附C₂H₆（在1 bar下，273、298和323 K时分别为24.9、18.9和13.4 cm³/g），同时显著降低C₂H₄的吸附（在1 bar下，273、298和323 K时分别为16.9、12.7和8.8 cm³/g）。在1 bar下，在273、298和323 K时，对C₂H₆/C₂H₄的IAST选择性分别为6.09、5.60和4.13，表明其对C₂H₆的选择性行为，这从实验突破测量中得到进一步证实。此外，用密度泛函理论进行的计算研究突出了电荷分布增强，导致C₂H₆π电子与Cu d电子之间的dπ-pπ共轭，从而显示与C₂H₆分子相比，与C₂H₆的相互作用能相对较高，为-37.23 kcal/mol，而与C₂H₄的相互作用能为-16.06 kcal/mol。
