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Title: Heteroatom substituted zeolite FAU with ultralow Al contents for liquid-phase oxidation catalysis

Journal Article · · Catalysis Science and Technology
DOI:https://doi.org/10.1039/c9cy01886g· OSTI ID:1803928
ORCiD logo [1];  [1];  [2];  [1]
  1. Univ. of Illinois at Urbana-Champaign, IL (United States). Dept. of Chemical and Biomolecular Engineering
  2. Univ. of Illinois at Urbana-Champaign, IL (United States). School of Chemical Sciences, NMR/EPR Laboratory

Heteroatom framework-substituted zeolites are important materials that enable shape- and size-selective catalysis. The efficacy of these materials for desired catalytic reactions depends critically on dispersive interactions between the microporous void of the zeolite and the reactant molecules stabilized within it. Here, we develop a post-synthetic method to synthesize base and transition metal-substituted (Ti, Nb, Ta, and Sn) FAU with ultralow Al contents (Si : Al > 900), which is confirmed using X-ray diffraction, elemental analysis, and N2 volumetric adsorption and 29Si MAS-NMR, DRUV-vis, and IR spectroscopic characterization. In this work, turnover rates for styrene (C8H8) epoxidation within Ti-FAU are 2- and 7-fold greater than in analogous Ti-BEA and Ti–SiO2, respectively; yet, turnover rates of H2O2 decomposition are similar for all three materials. Consequently, Ti-FAU gives greater rates and selectivities for this reaction than common Ti-bearing silicates. The mechanism for epoxidation remains constant for all Ti-silicates examined (i.e., Ti-FAU, Ti-BEA, and Ti–SiO2). Therefore, the improved performance of Ti-FAU reflects differences in activation free energies for epoxidation that show an enthalpic preference in Ti-FAU relative to Ti–SiO2 and an entropic gain relative to Ti-BEA. These results demonstrate the synthesis of M-FAU with ultralow Al contents are useful for catalytic reactions involving bulky reactants that can not occur in smaller pore zeotype materials (Ti-MFI), that exhibit deactivation due to changes in Ti-atom coordination (e.g., Ti–SiO2), and that are prone to losses catalyzed by residual Brønsted acid sites (e.g., epoxidations, oxidations, and isomerization reactions).

Research Organization:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Organization:
USDOE; USDOD; US Army Research Office (ARO)
Grant/Contract Number:
SC0020224; W911NF-19-1-0100
OSTI ID:
1803928
Alternate ID(s):
OSTI ID: 1580130
Journal Information:
Catalysis Science and Technology, Vol. 10, Issue 3; ISSN 2044-4753
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

References (68)

Delaminated zeolite precursors as selective acidic catalysts journal November 1998
Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report) journal October 2015
Synthesis of Niobium Silicate Molecular Sieves of the MFI Structure:  Evidence for Framework Incorporation of the Niobium Ion journal December 1998
Influence of Hydrophilicity on the Snβ-Catalyzed Baeyer-Villiger Oxidation of Cyclohexanone with Aqueous Hydrogen Peroxide journal December 2016
Synthesis and characterization of tantalum silicalite molecular sieves with MFI structure journal September 1999
Beyond shape selective catalysis with zeolites: Hydrophobic void spaces in zeolites enable catalysis in liquid water journal January 2013
Influence of confining environment polarity on ethanol dehydration catalysis by Lewis acid zeolites journal September 2018
Mesoporous Zr-Beta zeolites prepared by a post-synthetic strategy as a robust Lewis acid catalyst for the ring-opening aminolysis of epoxides journal January 2015
Incorporation of various heterometal atoms in CHA zeolites by hydrothermal conversion of FAU zeolite and their performance for selective catalytic reduction of NO x with ammonia journal July 2017
Catalytic thiophene oxidation by groups 4 and 5 framework-substituted zeolites with hydrogen peroxide: Mechanistic and spectroscopic evidence for the effects of metal Lewis acidity and solvent Lewis basicity journal August 2018
Ta(V)-Single Site BEA Zeolite by Two-Step Postsynthesis Method: Preparation and Characterization journal February 2010
Controlled insertion of tin atoms into zeolite framework vacancies and consequences for glucose isomerization catalysis journal December 2016
Impact of Specific Interactions Among Reactive Surface Intermediates and Confined Water on Epoxidation Catalysis and Adsorption in Lewis Acid Zeolites journal October 2019
Monosaccharide and disaccharide isomerization over Lewis acid sites in hydrophobic and hydrophilic molecular sieves journal December 2013
Distinct Catalytic Reactivity of Sn Substituted in Framework Locations and at Defect Grain Boundaries in Sn-Zeolites journal May 2019
Nanostructured Nb 2 O 5 catalysts journal January 2012
High-silica Hβ zeolites for catalytic hydration of hydrophobic epoxides and alkynes in water journal December 2018
Improving Stability of Zeolites in Aqueous Phase via Selective Removal of Structural Defects journal March 2016
Stability of Zeolites in Aqueous Phase Reactions journal August 2017
Characterization and catalytic activity of titanium containing SSZ-33 and aluminum-free zeolite beta journal August 1996
The Role of Outer-Sphere Surface Acidity in Alkene Epoxidation Catalyzed by Calixarene−Ti(IV) Complexes journal December 2007
Post-synthetic preparation of Sn-, Ti- and Zr-beta: a facile route to water tolerant, highly active Lewis acidic zeolites journal January 2014
Pyridine and ammonia as probes for FTIR analysis of solid acid catalysts journal January 1996
UV Resonance Raman Spectroscopic Identification of Titanium Atoms in the Framework of TS-1 Zeolite journal August 1999
Cooperative Effects between Hydrophilic Pores and Solvents: Catalytic Consequences of Hydrogen Bonding on Alkene Epoxidation in Zeolites journal January 2019
Experimental criterion for the absence of artifacts in the measurement of rates of heterogeneous catalytic reactions journal November 1982
Direct synthesis of H2O2 on PdZn nanoparticles: The impact of electronic modifications and heterogeneity of active sites journal December 2018
Studies on the Catalytic-Oxidation of Alkanes and Alkenes by Titanium Silicates journal September 1994
Preparation of B-free Ti-MWW through reversible structural conversion journal April 2002
An Ethoxy Intermediate in Ethanol Dehydration on Brønsted Acid Sites in Zeolite journal June 2005
Interrogating the Lewis Acidity of Metal Sites in Beta Zeolites with 15 N Pyridine Adsorption Coupled with MAS NMR Spectroscopy journal December 2016
Lewis Acid Zeolites for Biomass Conversion: Perspectives and Challenges on Reactivity, Synthesis, and Stability journal June 2016
Periodic Trends in Olefin Epoxidation over Group IV and V Framework-Substituted Zeolite Catalysts: A Kinetic and Spectroscopic Study journal May 2017
A procedure for the preparation of Ti-Beta zeolites for catalytic epoxidation with hydrogen peroxide journal January 2014
Mechanistic Study on the Lewis Acid Catalyzed Synthesis of 1,3-Butadiene over Ta-BEA Using Modulated Operando DRIFTS-MS journal September 2016
Consequences of Confinement for Alkene Epoxidation with Hydrogen Peroxide on Highly Dispersed Group 4 and 5 Metal Oxide Catalysts journal February 2018
Computational characterization of zeolite porous networks: an automated approach journal January 2011
Dehydration of Ethanol into Ethylene over Solid Acid Catalysts journal December 2005
Direct Synthesis and Characterization of Hydrophobic Aluminum-Free Ti−Beta Zeolite journal January 1998
Solvation and acid strength effects on catalysis by faujasite zeolites journal February 2012
Kinetic and spectroscopic evidence for reaction pathways and intermediates for olefin epoxidation on Nb in *BEA journal April 2017
TiO2 photocatalyst for degradation of organic compounds in water and air supported on highly hydrophobic FAU zeolite: Structural, sorptive, and photocatalytic studies journal January 2012
Deactivation mechanisms of tin-zeolites in biomass conversions journal January 2016
Conduction and Valence Band Positions of Ta 2 O 5 , TaON, and Ta 3 N 5 by UPS and Electrochemical Methods journal February 2003
Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations journal July 2001
New Nb and Ta–FAU zeolites—Direct synthesis, characterisation and surface properties journal December 2010
Experimental determination of the electronic band structure of SnO2 journal March 1998
Lewis Acid Catalysis Confined in Zeolite Cages as a Strategy for Sustainable Heterogeneous Hydration of Epoxides journal April 2016
Activity of Ti-Beta Catalyst for the Selective Oxidation of Alkenes and Alkanes journal January 1994
Improved Postsynthesis Strategy to Sn-Beta Zeolites as Lewis Acid Catalysts for the Ring-Opening Hydration of Epoxides journal July 2014
What Do the Niobium Framework Sites Look Like in Redox Zeolites? A Combined Theoretical and Experimental Investigation journal January 2010
The Effect of Water on the Adsorption of NO 2 in Na− and Ba−Y, FAU Zeolites:  A Combined FTIR and TPD Investigation journal March 2004
Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water journal March 2010
Synthesis of titanated chabazite with enhanced thermal stability by hydrothermal conversion of titanated faujasite journal October 2015
Synthesis of reaction‐adapted zeolites as methanol-to-olefins catalysts with mimics of reaction intermediates as organic structure‐directing agents journal July 2018
N-Doping of anodic TiO2 nanotubes using heat treatment in ammonia journal April 2006
Propylene oxide inhibits propylene epoxidation over Au/TS-1 journal September 2018
Postsynthesis and Effective Baeyer–Villiger Oxidation Properties of Hierarchical FAU-type Stannosilicate journal October 2016
Isomerization and β-scission reactions of alkanes on bifunctional metal-acid catalysts: Consequences of confinement and diffusional constraints on reactivity and selectivity journal December 2018
Synthesis of Itaconic Acid Ester Analogues via Self-Aldol Condensation of Ethyl Pyruvate Catalyzed by Hafnium BEA Zeolites journal April 2016
Local Environment Fine Structure in the 29Si NMR Spectra of Faujasite Zeolites journal April 1995
Periodic Trends in Highly Dispersed Groups IV and V Supported Metal Oxide Catalysts for Alkene Epoxidation with H 2 O 2 journal August 2015
The catalytic diversity of zeolites: confinement and solvation effects within voids of molecular dimensions journal January 2013
A comparative IR characterization of acidic sites on HY zeolite by pyridine and CO probes with silica–alumina and γ-alumina references journal January 2010
Large pore Ti-zeolites and mesoporous Ti-silicalites as catalysts for selective oxidation of organic sulfides journal January 1996
Predicting the Activity of Single Isolated Lewis Acid Sites in Solid Catalysts journal September 2006
Grafted Ta–calixarenes: Tunable, selective catalysts for direct olefin epoxidation with aqueous hydrogen peroxide journal October 2010
Adsorption properties of Fe-containing dealuminated BEA zeolites as revealed by FTIR spectroscopy journal June 2010