skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support

Abstract

Here, a heterobimetallic cobalt-aluminum complex was immobilized onto the metal organic framework NU-1000 using a simple solution-based deposition procedure. Characterization data are consistent with a maximum loading of a single Co-Al complex per Zr 6 node of NU-1000. Furthermore, the data support that the Co-Al bimetallic complex is evenly distributed throughout the NU-1000 particle, binds covalently to the Zr6 nodes, and occupies the NU-1000 apertures with the shortest internode distances (~8.5 Å). Heating the anchored Co-Al complex on NU-1000 at 300 °C for 1 h in air completely removes the organic ligand of the complex without affecting the structural integrity of the MOF support. We propose that a Co-Al oxide cluster is formed in place of the anchored complex in NU-1000 during heating. Collectively, the results suggest that well-defined heterobimetallic complexes can be effective precursors for installing two different metals simultaneously onto a MOF support. The CoAl-functionalized NU-1000 samples catalyze the oxidation of benzyl alcohol to benzaldehyde with tert-butyl hydroperoxide as a stoichiometric oxidant. Density functional theory calculations were performed to elucidate the detailed structures of the Co-Al active sites on the Zr 6-nodes, and a Co-mediated catalytic mechanism is proposed.

Authors:
 [1];  [1];  [1];  [2];  [1];  [1];  [1];  [3];  [1];  [3];  [2];  [1];  [1];  [2];  [1];  [3];  [3];  [2];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1356824
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 18; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Thompson, Anthony B., Pahls, Dale R., Bernales, Varinia, Gallington, Leighanne C., Malonzo, Camille D., Webber, Thomas, Tereniak, Stephen J., Wang, Timothy C., Desai, Sai Puneet, Li, Zhanyong, Kim, In Soo, Gagliardi, Laura, Penn, R. Lee, Chapman, Karena W., Stein, Andreas, Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., and Lu, Connie C.. Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b03244.
Thompson, Anthony B., Pahls, Dale R., Bernales, Varinia, Gallington, Leighanne C., Malonzo, Camille D., Webber, Thomas, Tereniak, Stephen J., Wang, Timothy C., Desai, Sai Puneet, Li, Zhanyong, Kim, In Soo, Gagliardi, Laura, Penn, R. Lee, Chapman, Karena W., Stein, Andreas, Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., & Lu, Connie C.. Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support. United States. doi:10.1021/acs.chemmater.6b03244.
Thompson, Anthony B., Pahls, Dale R., Bernales, Varinia, Gallington, Leighanne C., Malonzo, Camille D., Webber, Thomas, Tereniak, Stephen J., Wang, Timothy C., Desai, Sai Puneet, Li, Zhanyong, Kim, In Soo, Gagliardi, Laura, Penn, R. Lee, Chapman, Karena W., Stein, Andreas, Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., and Lu, Connie C.. 2016. "Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support". United States. doi:10.1021/acs.chemmater.6b03244. https://www.osti.gov/servlets/purl/1356824.
@article{osti_1356824,
title = {Installing heterobimetallic cobalt–aluminum single sites on a metal organic framework support},
author = {Thompson, Anthony B. and Pahls, Dale R. and Bernales, Varinia and Gallington, Leighanne C. and Malonzo, Camille D. and Webber, Thomas and Tereniak, Stephen J. and Wang, Timothy C. and Desai, Sai Puneet and Li, Zhanyong and Kim, In Soo and Gagliardi, Laura and Penn, R. Lee and Chapman, Karena W. and Stein, Andreas and Farha, Omar K. and Hupp, Joseph T. and Martinson, Alex B. F. and Lu, Connie C.},
abstractNote = {Here, a heterobimetallic cobalt-aluminum complex was immobilized onto the metal organic framework NU-1000 using a simple solution-based deposition procedure. Characterization data are consistent with a maximum loading of a single Co-Al complex per Zr6 node of NU-1000. Furthermore, the data support that the Co-Al bimetallic complex is evenly distributed throughout the NU-1000 particle, binds covalently to the Zr6 nodes, and occupies the NU-1000 apertures with the shortest internode distances (~8.5 Å). Heating the anchored Co-Al complex on NU-1000 at 300 °C for 1 h in air completely removes the organic ligand of the complex without affecting the structural integrity of the MOF support. We propose that a Co-Al oxide cluster is formed in place of the anchored complex in NU-1000 during heating. Collectively, the results suggest that well-defined heterobimetallic complexes can be effective precursors for installing two different metals simultaneously onto a MOF support. The CoAl-functionalized NU-1000 samples catalyze the oxidation of benzyl alcohol to benzaldehyde with tert-butyl hydroperoxide as a stoichiometric oxidant. Density functional theory calculations were performed to elucidate the detailed structures of the Co-Al active sites on the Zr6-nodes, and a Co-mediated catalytic mechanism is proposed.},
doi = {10.1021/acs.chemmater.6b03244},
journal = {Chemistry of Materials},
number = 18,
volume = 28,
place = {United States},
year = 2016,
month = 8
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

Save / Share:
  • Nickel/nanoporous carbon (Ni/NPC) composites are facilely prepared by direct pyrolysis of nonporous heterobimetallic zinc-nickel-terephthalate frameworks (Zn1-xNixMOF, x approximate to 0-1, MOF= metal-organic framework) at 1223 K in situ. Tailoring the Ni/Zn ratio creates densely populated and small Ni nanocrystals (Ni NCs) while maintaining sufficient porosity and surface area in the final product, which exhibits the largest activity factor (9.2 s(-1)g(-1)) and excellent stability toward 4-nitrophenol reduction.
  • Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. We resolved the atomic structure of Ni-oxo species deposited in the MOF NU-1000 through atomic layer deposition using local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and difference envelope density analysis, with electron microscopy imaging and computational modeling.
  • Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and differencemore » envelope density analysis, with electron microscopy imag-ing and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO xH y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield hetero-bimetallic metal-oxo nanowires. Finally, this bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering-resistance of these clusters during the hydrogenation of light olefins.« less
  • We report here the synthesis of robust and porous metal–organic frameworks (MOFs), M-MTBC (M = Zr or Hf), constructed from the tetrahedral linker methane-tetrakis(p-biphenylcarboxylate) (MTBC) and two types of secondary building units (SBUs): cubic M 82-O) 82-OH) 4 and octahedral M6(μ 3-O) 43-OH) 4. While the M 6-SBU is isostructural with the 12-connected octahedral SBUs of UiO-type MOFs, the M 8-SBU is composed of eight MIV ions in a cubic fashion linked by eight μ 2-oxo and four μ 2-OH groups. The metalation of Zr-MTBC SBUs with CoCl 2, followed by treatment with NaBEt 3H, afforded highlymore » active and reusable solid Zr-MTBC-CoH catalysts for the hydrogenation of alkenes, imines, carbonyls, and heterocycles. Zr-MTBC-CoH was impressively tolerant of a range of functional groups and displayed high activity in the hydrogenation of tri- and tetra-substituted alkenes with TON > 8000 for the hydrogenation of 2,3-dimethyl-2-butene. Our structural and spectroscopic studies show that site isolation of and open environments around the cobalt-hydride catalytic species at Zr 8-SBUs are responsible for high catalytic activity in the hydrogenation of a wide range of challenging substrates. MOFs thus provide a novel platform for discovering and studying new single-site base-metal solid catalysts with enormous potential for sustainable chemical synthesis.« less