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Title: Stable metal–organic framework-supported niobium catalysts

Journal Article · · Inorganic Chemistry
 [1];  [1];  [1];  [1];  [2];  [2];  [1];  [1];  [3]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)

In this study by developing structurally well-defined, supported oxide catalysts remains a significant challenge. Here, we report the grafting of Nb(V) oxide sites onto the nodes of the Zr-based metal organic framework (MOF) NU-1000 as a stable, well-defined catalyst support. Nb(V) oxide was deposited with loadings up to 1.6 mmol/g via two post-synthetic methods: atomic layer deposition in a MOF (AIM), and solution-phase grafting in a MOF (SIM). Difference envelope density (DED) measurements indicated that the two synthetic methods resulted in different local structures of the Nb(V) ions within NU-1000. Despite their high Nb(V) loadings, which were equivalent to >60% surface coverage, nearly all Nb(V) sites of the MOF-supported catalysts were active sites for alkene epoxidation, as confirmed by phenylphosphonic acid titration. The MOF-supported catalysts were more selective than the control Nb-ZrO2 catalyst for cyclohexene epoxidation with aqueous H2O2, and were far more active on a gravimetric basis.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; SC0012702
OSTI ID:
1332973
Journal Information:
Inorganic Chemistry, Vol. 55, Issue 22; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 75 works
Citation information provided by
Web of Science

References (66)

Atomically Dispersed Supported Metal Catalysts journal July 2012
Single-Site Heterogeneous Catalysts journal October 2005
Grafted Metallocalixarenes as Single-Site Surface Organometallic Catalysts journal December 2004
Synthesis of Supported Catalysts by Atomic Layer Deposition journal February 2012
A Sinter-Resistant Catalytic System Fabricated by Maneuvering the Selectivity of SiO 2 Deposition onto the TiO 2 Surface versus the Pt Nanoparticle Surface journal September 2013
Size-Selective Synthesis and Stabilization of Small Silver Nanoparticles on TiO 2 Partially Masked by SiO 2 journal January 2015
Kinetics of Heterogeneous Catalytic Reactions book January 1984
Hydrogen storage in metal–organic frameworks journal January 2009
De novo synthesis of a metal–organic framework material featuring ultrahigh surface area and gas storage capacities journal September 2010
Ultrahigh Porosity in Metal-Organic Frameworks journal July 2010
A new metal–organic framework with ultra-high surface area journal January 2014
Cooperative insertion of CO2 in diamine-appended metal-organic frameworks journal March 2015
Metal–Organic Framework Materials as Chemical Sensors journal September 2011
Metal–organic framework materials as catalysts journal January 2009
Enantioselective catalysis with homochiral metal–organic frameworks journal January 2009
Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2 journal March 2016
An Exceptionally Stable, Porphyrinic Zr Metal–Organic Framework Exhibiting pH-Dependent Fluorescence journal September 2013
Water Adsorption in Porous Metal–Organic Frameworks and Related Materials journal March 2014
Are Zr 6 -based MOFs water stable? Linker hydrolysis vs. capillary-force-driven channel collapse journal January 2014
Structural determination of a highly stable metal-organic framework with possible application to interim radioactive waste scavenging: Hf-UiO-66 journal September 2012
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
Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption journal May 2013
Chemical, thermal and mechanical stabilities of metal–organic frameworks journal February 2016
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
Single-Site Organozirconium Catalyst Embedded in a Metal–Organic Framework journal December 2015
Metal–Organic Framework Nodes as Nearly Ideal Supports for Molecular Catalysts: NU-1000- and UiO-66-Supported Iridium Complexes journal June 2015
Defining the Proton Topology of the Zr6-Based Metal–Organic Framework NU-1000 journal October 2014
Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework journal February 2016
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
Metal–Organic Framework Thin Films as Platforms for Atomic Layer Deposition of Cobalt Ions To Enable Electrocatalytic Water Oxidation journal December 2015
Atomically Precise Growth of Catalytically Active Cobalt Sulfide on Flat Surfaces and within a Metal–Organic Framework via Atomic Layer Deposition journal July 2015
Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation : Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation journal July 2016
Periodic Trends in Highly Dispersed Groups IV and V Supported Metal Oxide Catalysts for Alkene Epoxidation with H 2 O 2 journal August 2015
Application of niobium oxides as catalysts journal October 1990
Redox properties of niobium oxide catalysts journal April 1996
Niobium Compounds:  Preparation, Characterization, and Application in Heterogeneous Catalysis journal December 1999
Structural and Reactivity Properties of NbMCM-41: Comparison with That of Highly Dispersed Nb2O5/SiO2 Catalysts journal October 2001
Gel derived niobium–silicon mixed oxides: Characterization and catalytic activity for cyclooctene epoxidation journal September 2008
Frontiers in mesoporous molecular sieves containing niobium: From model materials to catalysts journal September 2012
Epoxidation with hydrogen peroxide of unsaturated fatty acid methyl esters over Nb(V)-silica catalysts journal October 2012
Niobium metallocenes deposited onto mesoporous silica via dry impregnation as catalysts for selective epoxidation of alkenes journal February 2013
Selective catalytic oxidations of cyclohexene, thioether and geraniol with hydrogen peroxide. Sensitivity to the structure of mesoporous niobosilicates journal January 2015
Influence of preparation methods and structure of niobium oxide-based catalysts in the epoxidation reaction journal October 2015
Cooperative Effect of Monopodal Silica-Supported Niobium Complex Pairs Enhancing Catalytic Cyclic Carbonate Production journal June 2015
The molecular structures and reactivity of supported niobium oxide catalysts journal October 1990
Epoxidation of cyclohexene on Nb-containing meso- and macroporous materials journal February 2003
Niobium–silica catalysts for the selective epoxidation of cyclic alkenes: the generation of the active site by grafting niobocene dichloride journal January 2013
Synthetic and mechanistic aspects of metal-catalysed epoxidations with hydroperoxides journal January 1980
Synthesis−Structure–Function Relationships of Silica-Supported Niobium(V) Catalysts for Alkene Epoxidation with H 2 O 2 journal August 2016
Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000 journal December 2015
Synthesis of nanocrystals of Zr-based metal–organic frameworks with csq-net: significant enhancement in the degradation of a nerve agent simulant journal January 2015
GSAS-II : the genesis of a modern open-source all purpose crystallography software package journal March 2013
Ab-initio structure determination of LiSbWO6 by X-ray powder diffraction journal March 1988
Crystallographic Computing System JANA2006: General features journal January 2014
Generation and applications of structure envelopes for porous metal–organic frameworks journal February 2013
Study of Guest Molecules in Metal–Organic Frameworks by Powder X-ray Diffraction: Analysis of Difference Envelope Density journal October 2014
Counting Active Sites on Titanium Oxide-Silica Catalysts for Hydrogen Peroxide Activation through In Situ Poisoning with Phenylphosphonic Acid journal October 2014
Chemistry of zirconia and its use in chromatography journal December 1993
Review: monoclinic zirconia, its surface sites and their interaction with carbon monoxide journal January 2015
Electronic spectroscopy of the niobium dimer molecule: Experimental and theoretical results journal December 1993
MOF Functionalization via Solvent-Assisted Ligand Incorporation: Phosphonates vs Carboxylates journal February 2015
Evaluation of Brønsted acidity and proton topology in Zr- and Hf-based metal–organic frameworks using potentiometric acid–base titration journal January 2016
Grafted Ta–calixarenes: Tunable, selective catalysts for direct olefin epoxidation with aqueous hydrogen peroxide journal October 2010
Optimization of cyclohexene epoxidation with dilute hydrogen peroxide and silica-supported titanium catalysts journal June 2003
Catalytic sites in silica-supported titanium catalysts: silsesquioxane complexes as models journal July 2005
Kinetic study of cyclooctene epoxidation with aqueous hydrogen peroxide over silica-supported calixarene–Ta(V) journal October 2010

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