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

Title: Steam‐Induced Coarsening of Single‐Unit‐Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis

Journal Article · · Angewandte Chemie
 [1];  [2];  [1];  [1];  [1];  [1];  [1];  [3];  [1];  [2];  [4]; ORCiD logo [5]
  1. Department of Chemical Engineering and Materials Science University of Minnesota 421 Washington Avenue SE Minneapolis MN 55455 USA
  2. Peter A. Rock Thermochemistry Laboratory NEAT-ORU University of California Davis Davis CA 95616 USA
  3. Department of Chemical Engineering Khalifa University of Science and Technology Habshan Building, Sas Al Nakhl Campus Abu Dhabi United Arab Emirates
  4. Department of Diagnostic and Biological Sciences University of Minnesota 515 Delaware St SE Minneapolis MN 55455 USA, Characterization Facility University of Minnesota 312 Church St Minneapolis MN 55455 USA
  5. Department of Chemical Engineering and Materials Science University of Minnesota 421 Washington Avenue SE Minneapolis MN 55455 USA, Department of Chemical and Biomolecular Engineering and Institute for NanoBioTechnology Johns Hopkins University 3400 N. Charles Street Baltimore MD 21218 USA, Applied Physics Laboratory Johns Hopkins University 11100 Johns Hopkins Road Laurel MD 20723 USA

Abstract Commonly used methods to assess crystallinity, micro‐/mesoporosity, Brønsted acid site density and distribution (in micro‐ vs. mesopores), and catalytic activity suggest nearly invariant structure and function for aluminosilicate zeolite MFI two‐dimensional nanosheets before and after superheated steam treatment. Yet, pronounced reaction rate decrease for benzyl alcohol alkylation with mesitylene, a reaction that cannot take place in the zeolite micropores, is observed. Transmission electron microscopy images reveal pronounced changes in nanosheet thickness, aspect ratio and roughness indicating that nanosheet coarsening and the associated changes in the external (mesoporous) surface structure are responsible for the changes in the external surface catalytic activity. Superheated steam treatment of hierarchical zeolites can be used to alter nanosheet morphology and regulate external surface catalytic activity while preserving micro‐ and mesoporosity, and micropore reaction rates.

Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0001004
OSTI ID:
1631505
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 132 Journal Issue: 24; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (57)

Impact of Aqueous Medium on Zeolite Framework Integrity journal April 2015
X-ray Imaging of Zeolite Particles at the Nanoscale: Influence of Steaming on the State of Aluminum and the Methanol-To-Olefin Reaction journal March 2012
Silicalite characterization. 2. IR spectroscopy of the interaction of carbon monoxide with internal and external hydroxyl groups journal June 1992
Physicochemical Characterization of Silicalite-1 Surface and Its Implications on Crystal Growth journal May 2003
3D Nanoscale Chemical Imaging of the Distribution of Aluminum Coordination Environments in Zeolites with Soft X-Ray Microscopy journal January 2013
Electron tomography and holography in materials science journal April 2009
Hierarchical Nanomanufacturing: From Shaped Zeolite Nanoparticles to High-Performance Separation Membranes journal October 2007
Tailoring and visualizing the pore architecture of hierarchical zeolites journal January 2015
Activity and selectivity differences of external Brønsted acid sites of single-unit-cell thick and conventional MFI and MWW zeolites journal December 2014
2,6-Di- tert- butylpyridine Sorption Approach to Quantify the External Acidity in Hierarchical Zeolites journal May 2014
Challenges on molecular aspects of dealumination and desilication of zeolites journal June 2014
Generation, Characterization, and Impact of Mesopores in Zeolite Catalysts journal January 2003
Intracrystalline rearrangement of constitutive water in hydrogen zeolite Y journal November 1967
Self-Pillared, Single-Unit-Cell Sn-MFI Zeolite Nanosheets and Their Use for Glucose and Lactose Isomerization journal July 2015
Factors that Determine Zeolite Stability in Hot Liquid Water journal September 2015
Catalytic Behavior of Brønsted Acid Sites in MWW and MFI Zeolites with Dual Meso- and Microporosity journal December 2010
Catalytic test reactions for the evaluation of hierarchical zeolites journal January 2016
Determining the location and nearest neighbours of aluminium in zeolites with atom probe tomography journal July 2015
A quantitative study of the structure–activity relationship in hierarchical zeolites using liquid‐phase reactions journal January 2019
X-ray Imaging of Zeolite Particles at the Nanoscale: Influence of Steaming on the State of Aluminum and the Methanol-To-Olefin Reaction journal March 2012
Imaging the effect of a hydrothermal treatment on the pore accessibility and acidity of large ZSM-5 zeolite crystals by selective staining journal January 2013
Hierarchically structured zeolites: synthesis, mass transport properties and applications journal January 2012
Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design journal January 2008
Architecture-Dependent Distribution of Mesopores in Steamed Zeolite Crystals as Visualized by FIB-SEM Tomography journal January 2011
Catalysis with hierarchical zeolites journal June 2011
Regioselectivity of Al–O Bond Hydrolysis during Zeolites Dealumination Unified by Brønsted–Evans–Polanyi Relationship journal November 2014
Spatial distribution, strength, and dealumination behavior of acid sites in nanocrystalline MFI zeolites and their catalytic consequences journal April 2012
Fast room temperature lability of aluminosilicate zeolites journal October 2019
Conceptual Frame Rationalizing the Self-Stabilization of H-USY Zeolites in Hot Liquid Water journal December 2014
Kinetic and Thermodynamic Studies of Silica Nanoparticle Dissolution journal August 2007
On the Synthesis and Adsorption Properties of Single-Unit-Cell Hierarchical Zeolites Made by Rotational Intergrowths journal September 2013
Detailed Reaction Paths for Zeolite Dealumination and Desilication From Density Functional Calculations journal December 2011
Water Interactions in Zeolite Catalysts and Their Hydrophobically Modified Analogues journal November 2015
Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts journal September 2009
Electron Tomography for Heterogeneous Catalysts and Related Nanostructured Materials journal May 2009
Simple quantification of zeolite acid site density by reactive gas chromatography journal January 2017
Ordered porous materials for emerging applications journal June 2002
Synthesis of Self-Pillared Zeolite Nanosheets by Repetitive Branching journal June 2012
Influence of steaming on the acidity and the methanol conversion reaction of HZSM-5 zeolite journal November 2013
Solvation and acid strength effects on catalysis by faujasite zeolites journal February 2012
Exploring the hierarchy of transport phenomena in hierarchical pore systems by NMR diffusion measurement journal December 2012
Zeolite Thin Films: From Computer Chips to Space Stations journal February 2010
Stability of Zeolites in Hot Liquid Water journal November 2010
Architecture-Dependent Distribution of Mesopores in Steamed Zeolite Crystals as Visualized by FIB-SEM Tomography journal January 2011
Solid-State NMR Detection, Characterization, and Quantification of the Multiple Aluminum Environments in US-Y Catalysts by 27 Al MAS and MQMAS Experiments at Very High Field journal June 2001
Detailed Reaction Paths for Zeolite Dealumination and Desilication From Density Functional Calculations journal December 2011
Thermochemistry of Pure-Silica Zeolites journal November 2000
Long-term steam stability of MWW structure zeolites (MCM-22 and ITQ-1) journal July 2014
Interdependence between porosity, acidity, and catalytic performance in hierarchical ZSM-5 zeolites prepared by post-synthetic modification journal December 2013
Two-Dimensional Zeolites: Current Status and Perspectives journal February 2014
Hierarchische Nanofertigung: von geformten Zeolithnanopartikeln zu hochleistungsfähigen Trennmembranen journal October 2007
Effect of Si/Al Ratio on the Catalytic Activity of Two‐Dimensional MFI Nanosheets in Aromatic Alkylation and Alcohol Etherification journal August 2019
Computer Visualization of Three-Dimensional Image Data Using IMOD journal January 1996
The Porosity, Acidity, and Reactivity of Dealuminated Zeolite ZSM-5 at the Single Particle Level: The Influence of the Zeolite Architecture journal November 2011
Two-dimensional zeolites in catalysis: current status and perspectives journal January 2016
2,6-Di-Tert-Butyl-Pyridine as a Probe Molecule to Measure External Acidity of Zeolites journal October 1998
Self-Pillared, Single-Unit-Cell Sn-MFI Zeolite Nanosheets and Their Use for Glucose and Lactose Isomerization journal July 2015

Similar Records

Steam-Induced Coarsening of Single-Unit-Cell MFI Zeolite Nanosheets and Its Effect on External Surface Brønsted Acid Catalysis
Journal Article · Sun Mar 01 00:00:00 EST 2020 · Angewandte Chemie (International Edition) · OSTI ID:1631505

Deactivation of Multilayered MFI Nanosheet Zeolite during Upgrading of Biomass Pyrolysis Vapors
Journal Article · Tue May 02 00:00:00 EDT 2017 · ACS Sustainable Chemistry & Engineering · OSTI ID:1631505

Ethanol and Water Adsorption in Conventional and Hierarchical All-Silica MFI Zeolites
Journal Article · Wed Nov 17 00:00:00 EST 2021 · ACS Physical Chemistry Au · OSTI ID:1631505

Related Subjects