TY - JOUR
T1 - Investigating the effect of metal nuclearity on activity for ethylene hydrogenation by metal-organic-framework-supported oxy-Ni(II) catalysts
AU - Wang, Qining
AU - Pengmei, Zihan
AU - Pandharkar, Riddhish
AU - Gagliardi, Laura
AU - Hupp, Joseph T.
AU - Notestein, Justin M.
N1 - Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (DE-SC0012702). This work made use of the IMSERC Crystallography facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), and Northwestern University. This work made use of the Keck-II facility of Northwestern University's NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the International Institute for Nanotechnology (IIN), and Northwestern's MRSEC program (NSF DMR-1720139).Metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center (QBIC).The REACT Core facility acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science program used for the purchase of the Nicolet 6700 FT-IR [DE-FG02-03ER15457] and BenchCAT reactor system [DE-SC0001329]. This work made use of the Advanced Photon Source of Argonne National Lab (ANL), at DND-CAT (Sector 5), which is supported by E.I. DuPont de Nemours & Co. Northwestern University, and The Dow Chemical Co.
Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (DE-SC0012702). This work made use of the IMSERC Crystallography facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), and Northwestern University. This work made use of the Keck-II facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the International Institute for Nanotechnology (IIN), and Northwestern's MRSEC program (NSF DMR-1720139).Metal analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center (QBIC).The REACT Core facility acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science program used for the purchase of the Nicolet 6700 FT-IR [DE-FG02-03ER15457] and BenchCAT reactor system [DE-SC0001329]. This work made use of the Advanced Photon Source of Argonne National Lab (ANL), at DND-CAT (Sector 5), which is supported by E.I. DuPont de Nemours & Co., Northwestern University, and The Dow Chemical Co.
Publisher Copyright:
© 2022 Elsevier Inc.
PY - 2022/3
Y1 - 2022/3
N2 - Metal-organic frameworks (MOFs), thanks to their well-defined coordination sites, are promising for studying catalytically active structures. To understand the effect of metal nuclearity in MOF-supported catalysts, we adjusted the nuclearity of oxy-Ni(II) supported on the zirconia-like nodes of MOF NU-1000 by modulating the Ni loading, where the organic linkers served to prevent node-to-node migration of grafted nickel ions. At the single-node level, we grafted auxiliary structural linkers, naphthalene dicarboxylate, to reduce the number of binding/grafting sites. We found higher catalytic rates at higher Ni loading for ethylene hydrogenation on a per-nickel-ion basis, despite the similar chemical environment of Ni(II) at different loadings; catalysts consisting mainly of pairs of nickel ions were more reactive than those of single nickel ions. These observations illustrate the need for at least two proximal nickel ions for effective catalysis – presumably one for hydrogen binding and heterolytic splitting and one for ethylene binding and activation.
AB - Metal-organic frameworks (MOFs), thanks to their well-defined coordination sites, are promising for studying catalytically active structures. To understand the effect of metal nuclearity in MOF-supported catalysts, we adjusted the nuclearity of oxy-Ni(II) supported on the zirconia-like nodes of MOF NU-1000 by modulating the Ni loading, where the organic linkers served to prevent node-to-node migration of grafted nickel ions. At the single-node level, we grafted auxiliary structural linkers, naphthalene dicarboxylate, to reduce the number of binding/grafting sites. We found higher catalytic rates at higher Ni loading for ethylene hydrogenation on a per-nickel-ion basis, despite the similar chemical environment of Ni(II) at different loadings; catalysts consisting mainly of pairs of nickel ions were more reactive than those of single nickel ions. These observations illustrate the need for at least two proximal nickel ions for effective catalysis – presumably one for hydrogen binding and heterolytic splitting and one for ethylene binding and activation.
KW - Active sites
KW - Catalyst nuclearity
KW - Ethylene hydrogenation
KW - MOFs
KW - Metal-organic frameworks
KW - Nickel catalysts
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U2 - 10.1016/j.jcat.2022.01.033
DO - 10.1016/j.jcat.2022.01.033
M3 - Article
AN - SCOPUS:85124544252
VL - 407
SP - 162
EP - 173
JO - Journal of Catalysis
JF - Journal of Catalysis
SN - 0021-9517
ER -