Han Yi, Sinnwell Michael A, Teat Simon J, Sushko Maria L, Bowden Mark E, Miller Quin R S, Schaef Herbert T, Liu Lili, Nie Zimin, Liu Jun, Thallapally Praveen K
Key Laboratory of Eco-Chemical Engineering College of Chemistry and Molecular Engineering Qingdao University of Science and Technology Qingdao 266042 P. R. China.
Pacific Northwest National Laboratory Richland WA 99352 USA.
Adv Sci (Weinh). 2019 Feb 8;6(7):1802056. doi: 10.1002/advs.201802056. eCollection 2019 Apr 3.
Efficient removal of heterocyclic organosulfur compounds from fuels can relieve increasingly serious environmental problems (e.g., gas exhaust contaminants triggering the formation of acid rain that can damage fragile ecological systems). Toward this end, novel metal-organic frameworks (MOFs)-based sorbent materials are designed and synthesized with distinct hard and soft metal building units, specifically {[YbCu(OH)(PyC)(HO)]·(NO)·S} (QUST-81) and {[YbO(HO)Cu(OH)(PyC)(HCOO)]·(NO)·S} (QUST-82), where HPyC = 4-Pyrazolecarboxylic acid. Exploiting the hard/soft duality, it is shown that the more stable QUST-82 can preserve desulfurization efficiency in the presence of competing nitrogen-containing contaminate. In addition, thermodynamically controlled single-crystal-to-single-crystal (SC-SC) phase transition is uncovered from QUST-81 to QUST-82, and in turn, mechanistic features are probed via X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, and ab initio molecular dynamics simulations.
从燃料中高效去除杂环有机硫化合物可以缓解日益严重的环境问题（例如，废气污染物引发酸雨形成，酸雨会破坏脆弱的生态系统）。为此，设计并合成了具有独特硬软金属构筑单元的新型金属有机框架（MOF）基吸附剂材料，具体为{[YbCu(OH)(PyC)(H₂O)]·(NO₃)·SO₄} （QUST - 81）和{[YbO(H₂O)Cu(OH)(PyC)(HCOO)]·(NO₃)·SO₄} （QUST - 82），其中HPyC = 4 - 吡唑羧酸。利用软硬对偶性表明，更稳定的QUST - 82在存在竞争性含氮污染物的情况下能够保持脱硫效率。此外，发现了从QUST - 81到QUST - 82的热力学控制的单晶到单晶（SC - SC）相变，进而通过X射线衍射、电感耦合等离子体原子发射光谱和从头算分子动力学模拟探究了其机理特征。
