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Title: Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis

Abstract

Understanding heterogeneous catalysts is a challenging pursuit due to surface site nonuniformity and aperiodicity in traditionally-used materials. One example is sulfated metal oxides, which function as highly-active catalysts and as supports for organometallic complexes. These applications are due to traits such as acidity, ability to act as a weakly coordinating ligand, and aptitude for promoting transformations via radical cation intermediates. Research is ongoing about the structural features of sulfated metal oxides that imbue the aforementioned properties, such as sulfate geometry and coordination. To better understand these materials, metal–organic frameworks (MOFs) have been targeted as structurally-defined analogs. Composed of inorganic nodes and organic linkers, MOFs possess features such as high porosity and crystallinity, which make them attractive for mechanistic studies of heterogeneous catalysts. In this work, a Zr6-based MOF NU-1000 is sulfated and characterized using atomically-precise techniques such as single crystal X-ray diffraction (SCXRD) in addition to diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Here, the dynamic nature of the sulfate binding motif is found to transition from monodentate, to bidentate, to tridentate depending on the degree of hydration, as supported by density functional theory (DFT) calculations. Heightened Brønsted acidity compared to the parent MOF was observed upon sulfation, and probedmore » through trimethylphosphine oxide (TMPO) physisorption, ammonia sorption, in-situ ammonia DRIFTS, and DFT studies. With the support structure benchmarked, an organoiridium complex was chemisorbed onto the sulfated MOF node and the efficacy of this supported catalyst was demonstrated for stoichiometric and catalytic activation of benzene-d6 and toluene with structure-activity relationships derived.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2];  [4]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [1];  [6]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [6]; ORCiD logo [5]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [7]; ORCiD logo [2]
+ Show Author Affiliations
  1. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Univ. of Minnesota, Minneapolis, MN (United States)
  4. Univ. of Chicago, IL (United States)
  5. Stony Brook Univ., NY (United States)
  6. Argonne National Lab. (ANL), Argonne, IL (United States)
  7. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Center (EFRC) (United States). Inorganometallic Catalyst Design Center (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); USDOD; National Science Foundation (NSF)
OSTI Identifier:
1962399
Grant/Contract Number:  
AC02-06CH11357; SC0014664; SC0012702; SC0001329; ECCS-2025633; DMR-1720139; DGE-1842165
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 144; Journal Issue: 37; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metal–Organic Frameworks; Sulfate; C–H Activation; Catalysis; Acidity; Anions; Ligands; Oxides; Transition Metals

Citation Formats

Syed, Zoha H., Mian, Mohammad Rasel, Patel, Roshan, Xie, Haomiao, Pengmei, Zihan, Chen, Zhihengyu, Son, Florencia A., Goetjen, Timothy A., Chapovetsky, Alon, Fahy, Kira M., Sha, Fanrui, Wang, Xingjie, Alayoglu, Selim, Kaphan, David M., Chapman, Karena W., Neurock, Matthew, Gagliardi, Laura, Delferro, Massimiliano, and Farha, Omar K. Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis. United States: N. p., 2022. Web. doi:10.1021/jacs.2c05290.
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Syed, Zoha H., Mian, Mohammad Rasel, Patel, Roshan, Xie, Haomiao, Pengmei, Zihan, Chen, Zhihengyu, Son, Florencia A., Goetjen, Timothy A., Chapovetsky, Alon, Fahy, Kira M., Sha, Fanrui, Wang, Xingjie, Alayoglu, Selim, Kaphan, David M., Chapman, Karena W., Neurock, Matthew, Gagliardi, Laura, Delferro, Massimiliano, & Farha, Omar K. Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis. United States. https://doi.org/10.1021/jacs.2c05290
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Syed, Zoha H., Mian, Mohammad Rasel, Patel, Roshan, Xie, Haomiao, Pengmei, Zihan, Chen, Zhihengyu, Son, Florencia A., Goetjen, Timothy A., Chapovetsky, Alon, Fahy, Kira M., Sha, Fanrui, Wang, Xingjie, Alayoglu, Selim, Kaphan, David M., Chapman, Karena W., Neurock, Matthew, Gagliardi, Laura, Delferro, Massimiliano, and Farha, Omar K. Sun . "Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis". United States. https://doi.org/10.1021/jacs.2c05290. https://www.osti.gov/servlets/purl/1962399.
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@article{osti_1962399,
title = {Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis},
author = {Syed, Zoha H. and Mian, Mohammad Rasel and Patel, Roshan and Xie, Haomiao and Pengmei, Zihan and Chen, Zhihengyu and Son, Florencia A. and Goetjen, Timothy A. and Chapovetsky, Alon and Fahy, Kira M. and Sha, Fanrui and Wang, Xingjie and Alayoglu, Selim and Kaphan, David M. and Chapman, Karena W. and Neurock, Matthew and Gagliardi, Laura and Delferro, Massimiliano and Farha, Omar K.},
abstractNote = {Understanding heterogeneous catalysts is a challenging pursuit due to surface site nonuniformity and aperiodicity in traditionally-used materials. One example is sulfated metal oxides, which function as highly-active catalysts and as supports for organometallic complexes. These applications are due to traits such as acidity, ability to act as a weakly coordinating ligand, and aptitude for promoting transformations via radical cation intermediates. Research is ongoing about the structural features of sulfated metal oxides that imbue the aforementioned properties, such as sulfate geometry and coordination. To better understand these materials, metal–organic frameworks (MOFs) have been targeted as structurally-defined analogs. Composed of inorganic nodes and organic linkers, MOFs possess features such as high porosity and crystallinity, which make them attractive for mechanistic studies of heterogeneous catalysts. In this work, a Zr6-based MOF NU-1000 is sulfated and characterized using atomically-precise techniques such as single crystal X-ray diffraction (SCXRD) in addition to diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Here, the dynamic nature of the sulfate binding motif is found to transition from monodentate, to bidentate, to tridentate depending on the degree of hydration, as supported by density functional theory (DFT) calculations. Heightened Brønsted acidity compared to the parent MOF was observed upon sulfation, and probed through trimethylphosphine oxide (TMPO) physisorption, ammonia sorption, in-situ ammonia DRIFTS, and DFT studies. With the support structure benchmarked, an organoiridium complex was chemisorbed onto the sulfated MOF node and the efficacy of this supported catalyst was demonstrated for stoichiometric and catalytic activation of benzene-d6 and toluene with structure-activity relationships derived.},
doi = {10.1021/jacs.2c05290},
journal = {Journal of the American Chemical Society},
number = 37,
volume = 144,
place = {United States},
year = {Sun Sep 11 00:00:00 EDT 2022},
month = {Sun Sep 11 00:00:00 EDT 2022}
}
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