TY - JOUR
T1 - Influence of 1-Butene Adsorption on the Dimerization Activity of Single Metal Cations on UiO-66 Nodes
AU - Löbbert, Laura
AU - Chheda, Saumil
AU - Zheng, Jian
AU - Khetrapal, Navneet
AU - Schmid, Julian
AU - Zhao, Ruixue
AU - Gaggioli, Carlo A.
AU - Camaioni, Donald M.
AU - Bermejo-Deval, Ricardo
AU - Gutiérrez, Oliver Y.
AU - Liu, Yue
AU - Siepmann, J. Ilja
AU - Neurock, Matthew
AU - Gagliardi, Laura
AU - Lercher, Johannes A.
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/1/18
Y1 - 2023/1/18
N2 - Grafting metal cations to missing linker defect sites in zirconium-based metal-organic frameworks, such as UiO-66, produces a uniquely well-defined and homotopic catalytically active site. We present here the synthesis and characterization of a group of UiO-66-supported metal catalysts, M-UiO-66 (M = Ni, Co, Cu, and Cr), for the catalytic dimerization of alkenes. The hydrogen-deuterium exchange via deuterium oxide adsorption followed by infrared spectroscopy showed that the last molecular water ligand desorbs from the sites after evacuation at 300 °C leading to M(OH)-UiO-66 structures. Adsorption of 1-butene is studied using calorimetry and density functional theory techniques to characterize the interactions of the alkene with metal cation sites that are found active for alkene oligomerization. For the most active Ni-UiO-66, the removal of molecular water from the active site significantly increases the 1-butene adsorption enthalpy and almost doubles the catalytic activity for 1-butene dimerization in comparison to the presence of water ligands. Other M-UiO-66 (M = Co, Cu, and Cr) exhibit 1-3 orders of magnitude lower catalytic activities compared to Ni-UiO-66. The catalytic activities correlate linearly with the Gibbs free energy of 1-butene adsorption. Density functional theory calculations probing the Cossee-Arlman mechanism for all metals support the differences in activity, providing a molecular level understanding of the metal site as the active center for 1-butene dimerization.
AB - Grafting metal cations to missing linker defect sites in zirconium-based metal-organic frameworks, such as UiO-66, produces a uniquely well-defined and homotopic catalytically active site. We present here the synthesis and characterization of a group of UiO-66-supported metal catalysts, M-UiO-66 (M = Ni, Co, Cu, and Cr), for the catalytic dimerization of alkenes. The hydrogen-deuterium exchange via deuterium oxide adsorption followed by infrared spectroscopy showed that the last molecular water ligand desorbs from the sites after evacuation at 300 °C leading to M(OH)-UiO-66 structures. Adsorption of 1-butene is studied using calorimetry and density functional theory techniques to characterize the interactions of the alkene with metal cation sites that are found active for alkene oligomerization. For the most active Ni-UiO-66, the removal of molecular water from the active site significantly increases the 1-butene adsorption enthalpy and almost doubles the catalytic activity for 1-butene dimerization in comparison to the presence of water ligands. Other M-UiO-66 (M = Co, Cu, and Cr) exhibit 1-3 orders of magnitude lower catalytic activities compared to Ni-UiO-66. The catalytic activities correlate linearly with the Gibbs free energy of 1-butene adsorption. Density functional theory calculations probing the Cossee-Arlman mechanism for all metals support the differences in activity, providing a molecular level understanding of the metal site as the active center for 1-butene dimerization.
UR - https://www.scopus.com/pages/publications/85146006131
U2 - 10.1021/jacs.2c12192
DO - 10.1021/jacs.2c12192
M3 - 文章
C2 - 36598430
AN - SCOPUS:85146006131
SN - 0002-7863
VL - 145
SP - 1407
EP - 1422
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 2
ER -