Pei Jiyan, Wang Jia-Xin, Shao Kai, Yang Yu, Cui Yuanjing, Wu Hui, Zhou Wei, Li Bin, Qian Guodong
State Key Laboratory of Silicon Materials, Cyrus Tang Center for Sensor Materials and Applications, Department of Materials Science & Engineering, Zhejiang University, Hangzhou 310027, China.
NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, MD 20899-6102, USA.
J Mater Chem A Mater. 2024 Aug;342. doi: 10.1016/j.seppur.2024.127011.
Realization of ethane-trapping materials for separating ethane (CH) from ethylene (CH) by adsorption, to potentially replace the energy-intensive cryogenic distillation technology, is of prime importance in the petrochemical industry. It is still very challenging to target CH-selective adsorbents with both high CH capture capacity and gas selectivity. Herein, we report that a crystal engineering or reticular chemistry strategy enables the control of pore size and functionality in a family of isomorphic metal-organic frameworks (MOFs) for boosting the CH uptake and selectivity simultaneously. By altering the carboxylic acid linker in Ni(bdc)(ted), we developed two novel isoreticular MOFs, Ni(ndc)(ted) and Ni(adc)(ted) (termed ZJU-120 and ZJU-121, respectively), in which the pore sizes and nonpolar aromatic rings can be finely engineered. We discover that activated ZJU-120a with the optimized pore size (4.4 Å) and aromatic rings exhibits both a very high CH uptake (96 cm g at 0.5 bar and 296 K) and CH/CH selectivity (2.74), outperforming most of the CH-selective MOFs reported. Computational studies indicate that the suitable pore size and more nonpolar aromatic rings on the pore surfaces of ZJU-120a mainly contribute to its exceptional CH uptake and selectivity. The breakthrough experiments demonstrate that ZJU-120a can efficiently separate CH from 50/50 and 10/90CH/CH mixtures under ambient conditions.
实现用于通过吸附从乙烯（CH₂=CH₂）中分离乙烷（CH₃CH₃）的乙烷捕获材料，以潜在地取代能源密集型低温蒸馏技术，在石化行业中至关重要。开发兼具高乙烷捕获能力和气体选择性的乙烷选择性吸附剂仍然极具挑战性。在此，我们报道一种晶体工程或网状化学策略能够控制同构金属有机框架（MOF）家族中的孔径和功能，以同时提高乙烷的吸附量和选择性。通过改变Ni(bdc)₂(ted)中的羧酸连接体，我们开发了两种新型同网状MOF，Ni(ndc)₂(ted)和Ni(adc)₂(ted)（分别称为ZJU - 120和ZJU - 121），其中孔径和非极性芳香环可以精细调控。我们发现具有优化孔径（4.4 Å）和芳香环的活化ZJU - 120a表现出非常高的乙烷吸附量（在0.5 bar和296 K下为96 cm³ g⁻¹）和乙烷/乙烯选择性（2.74），优于大多数已报道的乙烷选择性MOF。计算研究表明，ZJU - 120a孔表面合适的孔径和更多的非极性芳香环主要促成了其出色的乙烷吸附量和选择性。突破实验表明，ZJU - 120a在环境条件下能够有效地从50/50和10/90的乙烷/乙烯混合物中分离乙烷。
