Enhancing Selective Adsorption in a Robust Pillared-Layer Metal-Organic Framework via Channel Methylation for the Recovery of C2-C3 from Natural Gas.
Enhancing Selective Adsorption in a Robust Pillared-Layer Metal-Organic Framework via Channel Methylation for the Recovery of C2-C3 from Natural Gas.
复制标题
DOI：
10.1021/acsami.0c15267
复制
发表时间：
2020-11
影响因子：
9.5
通讯作者：
Yufang Wu;Zewei Liu;Junjie Peng;Xun Wang;Xingbang Zhou;Zhong Li
中科院分区：
文献类型：
--
作者：
Yufang Wu;Zewei Liu;Junjie Peng;Xun Wang;Xingbang Zhou;Zhong Li
在这里，我们报道了一种策略，通过水热合成方法构建了一个强大的超微孔金属有机框架（MOF）Ni（TMBDC）（DABCO）0.5，并研究了其吸附性能，从天然气中回收乙烷（C2）和丙烷（C3）。合成的Ni（TMBDC）（DABCO）0.5具有0.5 nm的均匀孔径的超微孔。结果表明，该催化剂对C3 H8和C2 H6具有较强的吸附作用，在1 kPa低压下C3 H8的吸附量可达2.80mmol/g，在10 kPa低压下C2 H6的吸附量可达2.93mmol/g，对乙烷和丙烷具有较强的吸附亲和力。增强的吸附可以归因于在样品的通道中的密集的和可接近的甲基和亚甲基基团的存在。大正则蒙特卡罗（GCMC）模拟也证实，从DABCO柱的亚甲基基团和从TMBDC配体的甲基基团在增强乙烷和丙烷的吸附中起着重要的作用。其理想吸附溶液理论（IAST）预测的C2 H6/CH 4选择性达到前所未有的29，远高于大多数MOFs的报道数据。稳定性测试证实，Ni（TMBDC）（DABCO）0.5的晶体结构在暴露于相对湿度为100%的潮湿空气数天后仍然保持完整。突破性实验表明，在常温下，Ni（TMBDC）（DABCO）0.5固定床可实现CH 4/C2 H6/C3 H8三元混合物的完全分离，显示出从天然气中回收低含量乙烷和丙烷的巨大潜力。
Here, we reported a strategy for channel methylation to construct a robust ultramicroporous metal-organic framework (MOF) Ni(TMBDC)(DABCO)0.5 through hydrothermal synthesis method and investigated its adsorption performance for recovering ethane (C2) and propane (C3) from natural gas. The as-synthesized Ni(TMBDC)(DABCO)0.5 featured ultramicroporosity with a uniform pore size of 0.5 nm. The resulting sample showed a strong adsorption interaction with C3H8 and C2H6, and its C3H8 adsorption capacity at a low pressure of 1 kPa was up to 2.80 mmol/g and its C2H6 adsorption capacity at a low pressure of 10 kPa reached as high as 2.93 mmol/g, exhibiting strong binding affinity for ethane and propane. The enhanced adsorption can be attributed to the presence of the dense and accessible methyl and methylene groups in the channels of the sample. Grand Canonical Monte Carlo (GCMC) simulations also confirmed that the methylene groups from the DABCO pillar and the methyl groups from the TMBDC ligand play an important role in enhancing the adsorption of ethane and propane. Its ideal adsorbed solution theory (IAST)-predicted selectivity of C2H6/CH4 reached unprecedentedly 29, much higher than most of the reported data for MOFs. The stability test confirmed that the crystal structure of Ni(TMBDC)(DABCO)0.5 still remained intact after it was exposed to moist air with a relative humidity of 100% for days. The breakthrough experiment demonstrated that the CH4/C2H6/C3H8 ternary mixture was completely separated using a fixed bed of Ni(TMBDC)(DABCO)0.5 at ambient temperature, showing a great potential for recovering the low content of ethane and propane from natural gas.