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

Title: Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework

Journal Article · · ACS Applied Materials and Interfaces

Here, direct control over structure and location of catalytic species deposited on amorphous supports represents a formidable challenge in heterogeneous catalysis. In contrast, a structurally well-defined, crystalline metal–organic framework (MOF) can be rationally designed using post-synthetic techniques to allow for desired structural or locational changes of deposited metal ions. Herein, naphthalene dicarboxylate linkers are incorporated in the MOF, NU-1000, to block the small cavities where few-atom clusters of cobalt oxide preferentially grow, inducing catalyst deposition towards hither-to ill-favored grafting sites orientated toward NU-1000’s mesoporous channels. Despite the different cobalt oxide location, the resulting material is still an active propane oxidative dehydrogenation catalyst at low temperature, reaching a turnover frequency of 0.68 ± 0.05 h–1 at 230 °C and confirming the utility of MOFs as crystalline supports to guide rational design of catalysts.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1435951
Journal Information:
ACS Applied Materials and Interfaces, Vol. 10, Issue 17; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 38 works
Citation information provided by
Web of Science

References (38)

Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition journal June 2017
Recent Developments in the Synthesis of Supported Catalysts journal June 2015
Tailoring the Catalytic Properties of Metal Nanoparticles via Support Interactions journal August 2016
Catalysis by Supported Single Metal Atoms journal November 2016
Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions journal November 2016
Controlling the Isolation and Pairing of Aluminum in Chabazite Zeolites Using Mixtures of Organic and Inorganic Structure-Directing Agents journal March 2016
Regulation of Framework Aluminum Siting and Acid Distribution in H-MCM-22 by Boron Incorporation and Its Effect on the Catalytic Performance in Methanol to Hydrocarbons journal March 2016
Conversion of Methanol to Olefins over H-ZSM-5 Zeolite: Reaction Pathway Is Related to the Framework Aluminum Siting journal September 2016
Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications journal February 2017
Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes journal August 2016
Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks journal October 2015
Highly Stereoselective Heterogeneous Diene Polymerization by Co-MFU-4 l : A Single-Site Catalyst Prepared by Cation Exchange journal August 2017
Selective Dimerization of Propylene with Ni-MFU-4 l journal April 2017
Mechanism of Single-Site Molecule-Like Catalytic Ethylene Dimerization in Ni-MFU-4 l journal January 2017
Single-Site Heterogeneous Catalysts for Olefin Polymerization Enabled by Cation Exchange in a Metal-Organic Framework journal August 2016
The Chemistry and Applications of Metal-Organic Frameworks journal August 2013
Gas/vapour separation using ultra-microporous metal–organic frameworks: insights into the structure/separation relationship journal January 2017
Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature journal November 2016
Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal–Organic Framework journal July 2017
Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework journal February 2016
Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal–Organic Framework for Ethylene Dimerization journal October 2016
Regioselective Atomic Layer Deposition in Metal–Organic Frameworks Directed by Dispersion Interactions journal October 2016
Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires journal July 2017
Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs journal July 2016
Molecular Retrofitting Adapts a Metal–Organic Framework to Extreme Pressure journal June 2017
Flexible Zirconium MOF as the Crystalline Sponge for Coordinative Alignment of Dicarboxylates journal February 2017
Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks journal November 2017
Versatile functionalization of the NU-1000 platform by solvent-assisted ligand incorporation journal January 2014
Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO2 Adsorption Studies
  • Deria, Pravas; Mondloch, Joseph E.; Tylianakis, Emmanuel
  • Journal of the American Chemical Society, Vol. 135, Issue 45, p. 16801-16804 https://doi.org/10.1021/ja408959g
journal October 2013
Functionalized Defects through Solvent-Assisted Linker Exchange: Synthesis, Characterization, and Partial Postsynthesis Elaboration of a Metal–Organic Framework Containing Free Carboxylic Acid Moieties journal January 2015
Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework
  • Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David
  • Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297 https://doi.org/10.1021/ja4050828
journal May 2013
Tailoring of network dimensionality and porosity adjustment in Zr- and Hf-based MOFs journal January 2013
Redox Chemistry of CoZSM-5 Zeolite journal January 1996
Study of Guest Molecules in Metal–Organic Frameworks by Powder X-ray Diffraction: Analysis of Difference Envelope Density journal October 2014
Critical Literature Review of the Kinetics for the Oxidative Dehydrogenation of Propane over Well-Defined Supported Vanadium Oxide Catalysts journal September 2014
Oxidative Dehydrogenation of Ethane: Common Principles and Mechanistic Aspects journal March 2013
Metal–Organic Framework Based upon the Synergy of a Brønsted Acid Framework and Lewis Acid Centers as a Highly Efficient Heterogeneous Catalyst for Fixed-Bed Reactions journal March 2015
Tandem catalysis with a bifunctional site-isolated Lewis acid–Brønsted base metal–organic framework, NH2-MIL-101(Al) journal January 2012

Cited By (2)

New linker installation in metal–organic frameworks journal January 2019
Tuning of the flexibility in metal–organic frameworks based on pendant arm macrocycles journal January 2019


Figures / Tables (5)