TY - JOUR
T1 - Computation-informed optimization of Ni(PyC)2 functionalization for noble gas separations
AU - Gantzler, Nickolas
AU - Kim, Min Bum
AU - Robinson, Alexander
AU - Terban, Maxwell W.
AU - Ghose, Sanjit
AU - Dinnebier, Robert E.
AU - York, Arthur Henry
AU - Tiana, Davide
AU - Simon, Cory M.
AU - Thallapally, Praveen K.
N1 - Publisher Copyright:
© 2022 The Author(s)
PY - 2022/9/21
Y1 - 2022/9/21
N2 - Our objective is to tune a “lead” metal-organic framework, Ni(PyC)2 (pyridine-4-carboxylate [PyC]), by functionalizing its PyC ligands to maximize its adsorptive selectivity for xenon over krypton at room temperature. To guide experiments, we (1) construct a library of Ni(PyC-X)2 (X = functional group) crystal structure models then (2) use molecular simulations to predict their noble gas adsorption and selectivity at room temperature. Motivated by our virtual screening, we synthesize Ni(PyC-m-NH2)2, determine its crystal structure by X-ray powder diffraction, measure its Xe, Kr, and Ar adsorption isotherms (298 K), and indeed find that its dilute Xe/Kr selectivity at 298 K (20) exceeds that of its parent Ni(PyC)2 (17). Corroborated by molecular models, in situ X-ray diffraction shows that Ni(PyC-m-NH2)2 organizes well-defined, Xe-tailored binding pockets along its one-dimensional channels. Our study illustrates the computation-informed optimization of a “lead” metal-organic framework.
AB - Our objective is to tune a “lead” metal-organic framework, Ni(PyC)2 (pyridine-4-carboxylate [PyC]), by functionalizing its PyC ligands to maximize its adsorptive selectivity for xenon over krypton at room temperature. To guide experiments, we (1) construct a library of Ni(PyC-X)2 (X = functional group) crystal structure models then (2) use molecular simulations to predict their noble gas adsorption and selectivity at room temperature. Motivated by our virtual screening, we synthesize Ni(PyC-m-NH2)2, determine its crystal structure by X-ray powder diffraction, measure its Xe, Kr, and Ar adsorption isotherms (298 K), and indeed find that its dilute Xe/Kr selectivity at 298 K (20) exceeds that of its parent Ni(PyC)2 (17). Corroborated by molecular models, in situ X-ray diffraction shows that Ni(PyC-m-NH2)2 organizes well-defined, Xe-tailored binding pockets along its one-dimensional channels. Our study illustrates the computation-informed optimization of a “lead” metal-organic framework.
KW - computational screening
KW - gas adsorption
KW - gas separations
KW - metal-organic frameworks
KW - MOFs
KW - molecular simulations
KW - noble gas adsorption
KW - Xe/Kr separations
UR - https://www.scopus.com/pages/publications/85138191028
U2 - 10.1016/j.xcrp.2022.101025
DO - 10.1016/j.xcrp.2022.101025
M3 - Article
AN - SCOPUS:85138191028
SN - 2666-3864
VL - 3
JO - Cell Reports Physical Science
JF - Cell Reports Physical Science
IS - 9
M1 - 101025
ER -