Nickel-Based Metal-Organic Frameworks for Coal-Bed Methane Purification with Record CH4/N2 Selectivity
Nickel-Based Metal-Organic Frameworks for Coal-Bed Methane Purification with Record CH4/N2 Selectivity
复制标题
用于煤层甲烷净化的镍基金属有机框架，具有创纪录的 CH4/N2 选择性
DOI：
10.1002/anie.202201017
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Yang Qing-Yuan
中科院分区：
文献类型：
--
作者：
Wang Shao-Min;Shivanna Mohana;Yang Qing-Yuan
煤层气的富集和净化提供了一种能源，并有助于抵消全球变暖。在这项工作中，我们展示了一种涉及调节孔径和孔化学的策略，以促进四种镍基配位网络中CH4/ n2混合物的分离，命名为Ni(ina)2,Ni(3 - ain)2,Ni(2 - ain)2和Ni(pba)2（其中ina=异烟酸，3 - ain=3 -氨基异烟酸，2 - ain=2 -氨基异烟酸，pba=4 -（4 -吡啶基）苯甲酸）。其中，Ni(ina)2和Ni(3‐ain)2由于合适的孔径（≈0.6和0.5 nm）和孔环境，可以有效地从n2中分离ch4，并具有最佳的性能。明确地，Ni(ina)2在环境条件下表现出最高的CH4/ n2选择性（15.8）和出色的CH4吸收率（40.8 cm3g−1），从而为所有报道的mof和传统吸附剂设定了新的基准。动态突破实验证实了ni (ina)2具有优异的CH4/ n2分离性能。在不同的CH4/ n2比下，Ni(ina)2选择性地从混合气体中提取甲烷，得到高纯度的CH4（99%）。理论计算和CH4负载单晶结构分析提供了对吸附/分离机制的关键见解。Ni(ina)2和Ni(3‐ain)2可以与甲烷形成丰富的分子间相互作用，表明孔壁与ch4分子之间具有很强的吸附亲和力。重要的是，Ni(ina)2具有良好的热稳定性和湿度稳定性，并且可以很容易地以低成本（每公斤25美元）扩大规模，这将对潜在的工业应用有价值。总之，这项工作为煤层气中ch4的选择性吸附提供了一种强有力的方法。
The enrichment and purification of coal‐bed methane provides a source of energy and helps offset global warming. In this work, we demonstrate a strategy involving the regulation of the pore size and pore chemistry to promote the separation of CH4/N2mixtures in four nickel‐based coordination networks, namedNi(ina)2,Ni(3‐ain)2,Ni(2‐ain)2, andNi(pba)2, (whereina=isonicotinic acid,3‐ain=3‐aminoisonicotinic acid,2‐ain=2‐aminoisonicotinic acid, andpba=4‐(4‐pyridyl)benzoic acid). Among them,Ni(ina)2andNi(3‐ain)2can effectively separate CH4from N2with top‐performing performance because of the suitable pore size (≈0.6 and 0.5 nm) and pore environment. Explicitly,Ni(ina)2exhibits the highest ever reported CH4/N2selectivity of 15.8 and excellent CH4uptake (40.8 cm3g−1) at ambient conditions, thus setting new benchmarks for all reported MOFs and traditional adsorbents. The exceptional CH4/N2separation performance ofNi(ina)2is confirmed by dynamic breakthrough experiments. Under different CH4/N2ratios,Ni(ina)2selectively extracts methane from the gaseous blend and produces a high purity of CH4(99 %). Theoretical calculations and CH4‐loading single‐crystal structure analysis provide critical insight into the adsorption/separation mechanism.Ni(ina)2andNi(3‐ain)2can form rich intermolecular interactions with methane, indicating a strong adsorption affinity between pore walls and CH4molecules. Importantly,Ni(ina)2has good thermal and moisture stability and can easily be scaled up at a low cost ($25 per kilogram), which will be valuable for potential industrial applications. Overall, this work provides a powerful approach for the selective adsorption of CH4from coal‐bed methane.