Abstract
The understanding of the catalyst-support interactions has been an important challenge in heterogeneous catalysis since the supports can play a vital role in controlling the properties of the active species and hence their catalytic performance. Herein, a series of isostructural mesoporous metal-organic frameworks (MOFs) based on transition metals, lanthanides, and actinides (Zr, Hf, Ce, Th) were investigated as supports for a vanadium catalyst. The vanadium species was coordinated to the oxo groups of the MOF node in a single-ion fashion, as determined by single-crystal X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, and diffuse reflectance UV-vis spectroscopy. The support effects of these isostructural MOFs were then probed using the aerobic oxidation of 4-methoxybenzyl alcohol as a model reaction. The turnover frequency was found to be correlated with the electronegativity and oxidation state of the metal cations on the supporting MOF nodes, highlighting an important consideration when designing catalyst supports.
Original language | English (US) |
---|---|
Pages (from-to) | 8306-8314 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 141 |
Issue number | 20 |
DOIs | |
State | Published - 2020 |
Funding
This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences (DE-SC0012702). EPR spectroscopy (M.D.K. and M.R.W.) was supported as part of the Center for Light Energy Activated Redox Processes, an EFRC funded by the DOE, Office of Science, Basic Energy Sciences (DE-SC0001059). X.W. gratefully acknowledges support from China Scholarship Council (CSC) during his visit to North-western University (201706150062). This work made use of the J. B. Cohen X-ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1720139) at the Materials Research Center of Northwestern University. This work made use of Keck-II facilities of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR-0521267); SHyNE Resource (NSF NNCI-1542205); and the State of Illinois and IIN.
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry
Fingerprint
Dive into the research topics of 'Vanadium Catalyst on Isostructural Transition Metal, Lanthanide, and Actinide Based Metal-Organic Frameworks for Alcohol Oxidation'. Together they form a unique fingerprint.Datasets
-
CCDC 1899941: Experimental Crystal Structure Determination
Wang, X. (Contributor), Zhang, X. (Contributor), Li, P. (Contributor), Otake, K.-I. (Contributor), Cui, Y. (Contributor), Lyu, J. (Contributor), Krzyaniak, M. D. (Contributor), Zhang, Y. (Contributor), Li, Z. (Contributor), Liu, J. (Contributor), Buru, C. T. (Contributor), Islamoglu, T. (Contributor), Wasielewski, M. R. (Contributor), Li, Z. (Contributor) & Farha, O. K. (Contributor), Cambridge Crystallographic Data Centre, 2019
DOI: 10.5517/ccdc.csd.cc21s1fb, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc21s1fb&sid=DataCite
Dataset
-
CCDC 1899942: Experimental Crystal Structure Determination
Wang, X. (Contributor), Zhang, X. (Contributor), Li, P. (Contributor), Otake, K.-I. (Contributor), Cui, Y. (Contributor), Lyu, J. (Contributor), Krzyaniak, M. D. (Contributor), Zhang, Y. (Contributor), Li, Z. (Contributor), Liu, J. (Contributor), Buru, C. T. (Contributor), Islamoglu, T. (Contributor), Wasielewski, M. R. (Contributor), Li, Z. (Contributor) & Farha, O. K. (Contributor), Cambridge Crystallographic Data Centre, 2019
DOI: 10.5517/ccdc.csd.cc21s1gc, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc21s1gc&sid=DataCite
Dataset
-
CCDC 1876021: Experimental Crystal Structure Determination
Wang, X. (Contributor), Zhang, X. (Contributor), Li, P. (Contributor), Otake, K.-I. (Contributor), Cui, Y. (Contributor), Lyu, J. (Contributor), Krzyaniak, M. D. (Contributor), Zhang, Y. (Contributor), Li, Z. (Contributor), Liu, J. (Contributor), Buru, C. T. (Contributor), Islamoglu, T. (Contributor), Wasielewski, M. R. (Contributor), Li, Z. (Contributor) & Farha, O. K. (Contributor), Cambridge Crystallographic Data Centre, 2019
DOI: 10.5517/ccdc.csd.cc20z4tz, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc20z4tz&sid=DataCite
Dataset