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Defect‐Engineered Ruthenium MOFs as Versatile Heterogeneous Hydrogenation Catalysts
Author(s) -
Epp Konstantin,
Luz Ignacio,
Heinz Werner R.,
Rapeyko Anastasia,
Llabrés i Xamena Francesc X.,
Fischer Roland A.
Publication year - 2020
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201902079
Subject(s) - catalysis , ruthenium , isomerization , chemistry , pyridine , solvent , hydrogen , linker , allylic rearrangement , combinatorial chemistry , molecule , hydrogen storage , benzene , organic chemistry , computer science , operating system
Ruthenium MOF [Ru 3 (BTC) 2 Y y ] ⋅ G g (BTC=benzene‐1,3,5‐tricarboxylate; Y=counter ions=Cl − , OH − , OAc − ; G=guest molecules=HOAc, H 2 O) is modified via a mixed‐linker approach, using mixtures of BTC and pyridine‐3,5‐dicarboxylate (PYDC) linkers, triggering structural defects at the distinct Ru 2 paddlewheel (PW) nodes. This defect‐engineering leads to enhanced catalytic properties due to the formation of partially reduced Ru 2 ‐nodes. Application of a hydrogen pre‐treatment protocol to the Ru−MOFs, leads to a further boost in catalytic activity. We study the benefits of (1) defect engineering and (2) hydrogen pre‐treatment on the catalytic activity of Ru−MOFs in the Meerwein‐Ponndorf‐Verley reaction and the isomerization of allylic alcohols to saturated ketones. Simple solvent washing could not avoid catalyst deactivation during recycling for the latter reaction, while hydrogen treatment prior to each catalytic run proved to facilitate materials recyclability with constant activity over five runs.