Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Identification of the strong Brønsted acid site in a metal–organic framework solid acid catalyst

Journal Article · · Nature Chemistry
 [1];  [1];  [1];  [2];  [3];  [4];  [1];  [1];  [1];  [1];  [1];  [3];  [1];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Stanford Univ., CA (United States)
  3. Univ. of California, Berkeley, CA (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
It remains cumbersome to understand the surface of solid acid catalysts at the molecular level, despite their importance for industrial catalytic applications. A sulfated zirconium-based metal-organic framework, MOF-808-SO4, was previously shown to be a strong solid Brønsted acid material. In this report, we probe the origin of its acidity through an array of spectroscopic, crystallographic and computational characterization techniques. The strongest Brønsted acid site is demonstrated to consist of a specific arrangement of adsorbed water and sulfate moieties on the zirconium clusters. When a water molecule adsorbs to one zirconium atom, it participates in a hydrogen bond with a sulfate moiety that is chelated to a neighbouring zirconium atom; this motif, in turn, results in the presence of a strongly acidic proton. On dehydration, the material loses its acidity. The hydrated sulfated MOF exhibits a good catalytic performance for the dimerization of isobutene (2-methyl-1-propene), and achieves a 100% selectivity for C8 products with a good conversion efficiency.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
German Research Foundation (DFG); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; SC0001015
OSTI ID:
1542363
Journal Information:
Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 2 Vol. 11; ISSN 1755-4330
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

References (33)

Definitive Molecular Level Characterization of Defects in UiO-66 Crystals journal August 2015
A Unified pH Scale for All Phases journal August 2010
“Heterogeneity within Order” in Metal-Organic Frameworks journal January 2015
Definitive Molecular Level Characterization of Defects in UiO-66 Crystals journal August 2015
One-Step Synthesis and Characterization of Zirconia-Sulfate Aerogels as Solid Superacids journal November 1994
Investigation of the Acidic Properties of ZrO2 Modified by SO2−4 Anions journal November 1994
Acid Sites in Sulfated and Metal-Promoted Zirconium Dioxide Catalysts journal February 1995
An NMR study of acid sites on sulfated-zirconia catalysts using trimethylphosphine as a probe journal January 1994
High-resolution double-quantum NMR spectroscopy of homonuclear spin pairs and proton connectivities in solids journal September 1995
An infrared study of sulfated zirconia journal March 1988
Nature of hydrous zirconia and sulfated hydrous zirconia journal June 1994
Kinetic study of isobutene dimerization catalyzed by a macroporous sulphonic acid resin journal November 1993
17O and 1H NMR study of the tetranuclear hydroxo zirconium complex in aqueous solution journal April 1993
Sulfated zirconia and its modified versions as promising catalysts for industrial processes journal December 1999
A solid-state NMR, FT-IR and TPD study on acid properties of sulfated and metal-promoted zirconia: Influence of promoter and sulfation treatment journal August 2006
Sulfation of metal–organic frameworks: Opportunities for acid catalysis and proton conductivity journal July 2011
The surface structure of sulfated zirconia: Studies of XPS and thermal analysis journal February 2006
Sequence-Dependent Materials journal March 2017
Conversion of Isobutylene to Octane-Booster Compounds after Methyl tert -Butyl Ether Phaseout: The Role of Heterogeneous Catalysis journal October 2016
Process Analysis for Dimerization of Isobutene by Reactive Distillation journal March 2006
Gas-phase reactions of weak Broensted bases I-, PO3-, HSO4-, FSO3-, and CF3SO3- with strong Broensted acids H2SO4, FSO3H, and CF3SO3H. A quantitative intrinsic superacidity scale for the sulfonic acids XSO3H (X = HO, F, and CF3) journal May 1992
Tandem Hydroformylation/Hydrogenation of Alkenes to Normal Alcohols Using Rh/Ru Dual Catalyst or Ru Single Component Catalyst journal November 2012
Water Adsorption in Porous Metal–Organic Frameworks and Related Materials journal March 2014
Superacidity in Sulfated Metal–Organic Framework-808 journal September 2014
The Surface Structure of Sulfated Zirconia:  Periodic ab Initio Study of Sulfuric Acid Adsorbed on ZrO 2 (101) and ZrO 2 (001) journal December 1998
An Investigation of Hydrogen Bonding in Benzoxazine Dimers by Fast Magic-Angle Spinning and Double-Quantum 1 H NMR Spectroscopy journal November 1998
Theoretical Predictions of 31 P NMR Chemical Shift Threshold of Trimethylphosphine Oxide Absorbed on Solid Acid Catalysts journal April 2008
31 P Chemical Shift of Adsorbed Trialkylphosphine Oxides for Acidity Characterization of Solid Acids Catalysts journal August 2008
Microcalorimetric Characterization of Structural and Chemical Heterogeneity of Superacid SO 4 /ZrO 2 Systems † journal March 1997
Organic syntheses catalyzed by superacidic metal oxides: sulfated zirconia and related compounds journal January 2009
Acid properties of solid acid catalysts characterized by solid-state 31P NMR of adsorbed phosphorous probe molecules journal January 2011
Structural disorder in molecular framework materials journal January 2013
Sulfated Zirconia-Based Strong Solid-Acid Catalysts: Recent Progress journal August 1996

Cited By (18)

A solvent-assisted ligand exchange approach enables metal-organic frameworks with diverse and complex architectures journal February 2020
Developing two-dimensional solid superacids with enhanced mass transport, extremely high acid strength and superior catalytic performance journal January 2019
An Ultrastable Matryoshka [Hf 13 ] Nanocluster as a Luminescent Sensor for Concentrated Alkali and Acid journal September 2019
An Ultrastable Matryoshka [Hf 13 ] Nanocluster as a Luminescent Sensor for Concentrated Alkali and Acid journal November 2019
Temperature‐induced formation of two dinuclear dysprosium complexes with different magnetic properties journal May 2020
Reversible Structural Transformations of Metal–Organic Frameworks as Artificial Switchable Catalysts for Dynamic Control of Selectively Cyanation Reaction journal July 2019
Metal–Helix Frameworks Formed by μ 3 ‐NO 3 − with Different Orientations and Connected to a Heterometallic Cu II 10 Dy III 2 Folded Cluster journal July 2019
Solid-state NMR studies of the acidity of functionalized metal-organic framework UiO-66 materials journal July 2019
Efficient Production of Ethyl Levulinate from Furfuryl Alcohol Catalyzed by Modified Zirconium Phosphate journal April 2019
Discovery of Zr-based metal-organic polygon: Unveiling new design opportunities in reticular chemistry journal May 2020
Synthesis, characterization, and post-synthetic modification of a micro/mesoporous zirconium–tricarboxylate metal–organic framework: towards the addition of acid active sites journal January 2019
Enhanced proton conductivity of a MOF-808 framework through anchoring organic acids to the zirconium clusters by post-synthetic modification journal January 2019
Acid properties of organosiliceous hybrid materials based on pendant (fluoro)aryl-sulfonic groups through a spectroscopic study with probe molecules journal January 2019
Self-solidification ionic liquids as heterogeneous catalysts for biodiesel production journal January 2019
A series of dysprosium-based hydrogen-bonded organic frameworks (Dy–HOFs): thermally triggered off → on conversion of a single-ion magnet journal January 2019
Alterations to secondary building units of metal–organic frameworks for the development of new functions journal January 2020
The crucial roles of guest water in a biocompatible coordination network in the catalytic ring-opening polymerization of cyclic esters: a new mechanistic perspective journal January 2020
POWGEN: rebuild of a third-generation powder diffractometer at the Spallation Neutron Source journal October 2019

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY