TY - JOUR
T1 - Thermal Defect Engineering of Precious Group Metal-Organic Frameworks
T2 - A Case Study on Ru/Rh-HKUST-1 Analogues
AU - Heinz, Werner R.
AU - Agirrezabal-Telleria, Iker
AU - Junk, Raphael
AU - Berger, Jan
AU - Wang, Junjun
AU - Sharapa, Dmitry I.
AU - Gil-Calvo, Miryam
AU - Luz, Ignacio
AU - Soukri, Mustapha
AU - Studt, Felix
AU - Wang, Yuemin
AU - Wöll, Christof
AU - Bunzen, Hana
AU - Drees, Markus
AU - Fischer, Roland A.
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/9/9
Y1 - 2020/9/9
N2 - A methodology is introduced for controlled postsynthetic thermal defect engineering (TDE) of precious group metal-organic frameworks (PGM-MOFs). The case study is based on the Ru/Rh analogues of the archetypical structure [Cu3(BTC)2] (HKUST-1; BTC = 1,3,5-benzenetricarboxylate). Quantitative monitoring of the TDE process and extensive characterization of the samples employing a complementary set of analytical and spectroscopic techniques reveal that the compositionally very complex TDE-MOF materials result from the elimination and/or fragmentation of ancillary ligands and/or linkers. TDE involves the preferential secession of acetate ligands, intrinsically introduced via coordination modulation during synthesis, and the gradual decarboxylation of ligator sites of the framework linker BTC. Both processes lead to modified Ru/Rh paddlewheel nodes. These nodes exhibit a lowered average oxidation state and more accessible open metal centers, as deduced from surface-ligand IR spectroscopy using CO as a probe and supported by density functional theory (DFT)-based computations. The monometallic and the mixed-metal PGM-MOFs systematically differ in their TDE properties and, in particular in the hydride generation ability (HGA). This latter property is an important indicator for the catalytic activity of PGM-MOFs, as demonstrated by the ethylene dimerization reaction to 1-butene.
AB - A methodology is introduced for controlled postsynthetic thermal defect engineering (TDE) of precious group metal-organic frameworks (PGM-MOFs). The case study is based on the Ru/Rh analogues of the archetypical structure [Cu3(BTC)2] (HKUST-1; BTC = 1,3,5-benzenetricarboxylate). Quantitative monitoring of the TDE process and extensive characterization of the samples employing a complementary set of analytical and spectroscopic techniques reveal that the compositionally very complex TDE-MOF materials result from the elimination and/or fragmentation of ancillary ligands and/or linkers. TDE involves the preferential secession of acetate ligands, intrinsically introduced via coordination modulation during synthesis, and the gradual decarboxylation of ligator sites of the framework linker BTC. Both processes lead to modified Ru/Rh paddlewheel nodes. These nodes exhibit a lowered average oxidation state and more accessible open metal centers, as deduced from surface-ligand IR spectroscopy using CO as a probe and supported by density functional theory (DFT)-based computations. The monometallic and the mixed-metal PGM-MOFs systematically differ in their TDE properties and, in particular in the hydride generation ability (HGA). This latter property is an important indicator for the catalytic activity of PGM-MOFs, as demonstrated by the ethylene dimerization reaction to 1-butene.
KW - HKUST-1
KW - Rh-BTC
KW - Ru-BTC
KW - ethylene dimerization
KW - metal-organic framework
KW - precious metal
KW - solid-gas interactions
KW - thermal defect engineering
UR - http://www.scopus.com/inward/record.url?scp=85090870024&partnerID=8YFLogxK
U2 - 10.1021/acsami.0c10721
DO - 10.1021/acsami.0c10721
M3 - Article
C2 - 32791827
AN - SCOPUS:85090870024
SN - 1944-8244
VL - 12
SP - 40635
EP - 40647
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 36
ER -