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Vapor Phase Installation of CpCo(CO)2 in MOF‐808

Journal Article · · Advanced Materials Interfaces
 [1];  [2];  [1];  [1];  [3];  [1]
  1. Argonne National Laboratory (ANL), Argonne, IL (United States)
  2. Univ. of Illinois, Chicago, IL (United States)
  3. Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
+ Show Author Affiliations
Metal-organic frameworks (MOFs), including MOF-808 present an opportunity for vapor phase installation of reactive centers that may serve as uniform sites for precision catalysis. The mechanism of cobalt installation in MOF-808 through atomic layer deposition (ALD) upon CpCo(CO)2 exposure is investigated through in situ FTIR spectroscopy complemented by density functional theory modeling. The role of subsequent H2O exposure in the hydrolysis of carbonyl and cyclopentadienyl ligands to complete the installation is also investigated. In situ FTIR study reveals that upon exposure of CpCo(CO)2 to MOF-808 at 115 °C, a long-lived, stable intermediate is formed that presents carbonyl stretching vibrations similar to the undissociated precursor that are attributed to multiple chemisorbed carbonyl complexes. In MOF-808, cobalt species are initially absorbed near the BTC linker rather than directly on the nodes, revealing the importance of non-covalent interactions in the installation process. DFT suggests that H2O exposure promotes carbonyl elimination but leaves a cyclopentadienyl-capped cobalt that is more stable than the complete hydrolysis product. The simulations are consistent with cobalt installation in MOF-808 using CpCo(CO)2 and H2O at 115 °C and further consistent with the lack of ALD thin film deposition of cobalt oxide thin films on planar supports.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
2574935
Journal Information:
Advanced Materials Interfaces, Journal Name: Advanced Materials Interfaces Journal Issue: 14 Vol. 12; ISSN 2196-7350
Publisher:
Wiley-VCHCopyright Statement
Country of Publication:
United States
Language:
English

References (41)

Molecular Organometallic Chemistry on Surfaces: Reactivity of Metal Carbonyls on Metal Oxides journal September 1988
Effect of the damping function in dispersion corrected density functional theory journal March 2011
In Situ Infrared Spectroscopic and Gravimetric Characterisation of the Solvent Removal and Dehydroxylation of the Metal Organic Frameworks UiO-66 and UiO-67 journal May 2013
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Photochemistry of η5 cylclopentadienylcobalt) tricarbonyl, tris(η5-cyclopentadienylcobalt monocarbonyl) and tetra(η5-cyclopentadienylcobalt) dicarbonyl* journal September 1975
Infrared laser spectroscopy of jet-cooled cyclopentadienyl cobalt dicarbonyl journal October 1997
Electron impact ionization of cobalt-tricarbonyl-nitrosyl, cyclopentadienyl-cobalt-dicarbonyl and biscyclopentadienyl-cobalt: appearance energies, bond energies and enthalpies of formation journal February 2003
Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications journal February 2017
Small Molecules, Big Effects: Tuning Adsorption and Catalytic Properties of Metal–Organic Frameworks journal February 2021
Cobalt Metal ALD: Understanding the Mechanism and Role of Zinc Alkyl Precursors as Reductants for Low-Resistivity Co Thin Films journal June 2021
Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition journal June 2015
Synthetic Access to Atomically Dispersed Metals in Metal–Organic Frameworks via a Combined Atomic-Layer-Deposition-in-MOF and Metal-Exchange Approach journal February 2016
Sequential Infiltration Synthesis of Electronic Materials: Group 13 Oxides via Metal Alkyl Precursors journal June 2019
Brønsted Basicity in Metal–Organic Framework-808 and Its Application in Base-Free Catalysis journal June 2018
Computationally Guided Discovery of a Catalytic Cobalt-Decorated Metal–Organic Framework for Ethylene Dimerization journal October 2016
Molecular Dynamics and Surface Interactions of Nickelocene Adsorbed on Silica: A Paramagnetic Solid-State NMR Study journal June 2022
Thermal Chemistry of Metal Organic Compounds Adsorbed on Oxide Surfaces journal November 2019
Ferrocene Adsorbed on Silica and Activated Carbon Surfaces: A Solid-State NMR Study of Molecular Dynamics and Surface Interactions journal March 2020
Revisiting Vibrational Spectroscopy to Tackle the Chemistry of Zr6O8 Metal-Organic Framework Nodes journal May 2022
Metal–Organic Framework Thin Films as Platforms for Atomic Layer Deposition of Cobalt Ions To Enable Electrocatalytic Water Oxidation journal December 2015
Metal–Organic Framework-Encaged Monomeric Cobalt(III) Hydroperoxides Enable Chemoselective Methane Oxidation to Methanol journal August 2022
Tailoring and Identifying Brønsted Acid Sites on Metal Oxo-Clusters of Metal–Organic Frameworks for Catalytic Transformation journal January 2023
Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature journal November 2016
Binuclear Cyclopentadienylcobalt Carbonyls:  Comparison with Binuclear Iron Carbonyls journal July 2005
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
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953
journal October 2008
Neighboring Zn–Zr Sites in a Metal–Organic Framework for CO 2 Hydrogenation journal June 2021
The Synthesis Science of Targeted Vapor-Phase Metal–Organic Framework Postmodification journal December 2019
Site of attack in the gas-phase reactions of negative ions with (.eta.5-cyclopentadienyl)dicarbonylcobalt(I) journal July 1992
Chemical, thermal and mechanical stabilities of metal–organic frameworks journal February 2016
Identification of the strong Brønsted acid site in a metal–organic framework solid acid catalyst journal November 2018
Evaluation of Brønsted acidity and proton topology in Zr- and Hf-based metal–organic frameworks using potentiometric acid–base titration journal January 2016
Unravelling the local structure of catalytic Fe-oxo clusters stabilized on the MOF-808 metal organic-framework journal January 2020
The state of the field: from inception to commercialization of metal–organic frameworks journal January 2021
Metal–organic framework materials as catalysts journal January 2009
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
Implementation strategies in phonopy and phono3py journal June 2023
Ab initiomolecular dynamics for liquid metals journal January 1993
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
Atomic layer deposition of cobalt oxide thin films using cyclopentadienylcobalt dicarbonyl and ozone at low temperatures journal December 2012

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Related Subjects

ALD
ALD in MOF
atomic layer deposition
catalysis
in situ
metal organic framework