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Title: Selective active site placement in Lewis acid zeolites and implications for catalysis of oxygenated compounds

Abstract

The selective incorporation of isolated framework Lewis acid sites at specific crystallographic positions in high-silica zeolites was achieved by applying a rationalized post-synthetic grafting methodology. The removal of framework Ge atoms from a Ge-BEC zeolite with low concentrations of Ge in the framework (Si/Ge ~ 150) followed by grafting allows the synthesis of Sn-BEC zeolites with Sn atoms positionally biased into the double-4-ring (D4R) crystallographic positions of the BEC framework. Spectroscopic characterization using solid-state nuclear magnetic resonance (NMR) coupled with theoretical calculations revealed that Sn atoms preferentially form open Sn sites in the D4R of Sn-BEC. This observation was supported by IR spectra of adsorbed deuterated acetonitrile (CD3CN), a known titrant of Sn sites in zeolites. The catalytic implications of selective incorporation of open Sn sites in Sn-BEC were probed using the Meerwein–Ponndorf–Verley–Oppenauer (MPVO) reaction. Although the MPVO turnover rates normalized by the total number of open Sn sites were comparable on Sn-BEC and a conventional Sn-Beta catalyst synthesized in fluoride media (Sn-Beta(F)), Sn-BEC demonstrated higher per gram reaction rates because of its larger fraction of open sites compared to Sn-Beta(F). These results highlight the advantage of placing active sites in targeted locations within a zeolite structure. The methodology presentedmore » here to selectively place catalytic active sites via sacrificial heteroatoms, such as Ge, can be generalized for the design of many other tetrahedrally-coordinated metal-containing zeolites.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Instituto de Tecnología Química, Universitat Politècnica de València-Consejo Superior de Investigaciones Científicas, 46022 València, Spain
  2. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, USA
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1660480
Alternate Identifier(s):
OSTI ID: 1701731
Grant/Contract Number:  
SC0016214
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 37; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rodríguez-Fernández, Aída, Di Iorio, John R., Paris, Cecilia, Boronat, Mercedes, Corma, Avelino, Román-Leshkov, Yuriy, and Moliner, Manuel. Selective active site placement in Lewis acid zeolites and implications for catalysis of oxygenated compounds. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0SC03809A.
Rodríguez-Fernández, Aída, Di Iorio, John R., Paris, Cecilia, Boronat, Mercedes, Corma, Avelino, Román-Leshkov, Yuriy, & Moliner, Manuel. Selective active site placement in Lewis acid zeolites and implications for catalysis of oxygenated compounds. United Kingdom. https://doi.org/10.1039/D0SC03809A
Rodríguez-Fernández, Aída, Di Iorio, John R., Paris, Cecilia, Boronat, Mercedes, Corma, Avelino, Román-Leshkov, Yuriy, and Moliner, Manuel. Wed . "Selective active site placement in Lewis acid zeolites and implications for catalysis of oxygenated compounds". United Kingdom. https://doi.org/10.1039/D0SC03809A.
@article{osti_1660480,
title = {Selective active site placement in Lewis acid zeolites and implications for catalysis of oxygenated compounds},
author = {Rodríguez-Fernández, Aída and Di Iorio, John R. and Paris, Cecilia and Boronat, Mercedes and Corma, Avelino and Román-Leshkov, Yuriy and Moliner, Manuel},
abstractNote = {The selective incorporation of isolated framework Lewis acid sites at specific crystallographic positions in high-silica zeolites was achieved by applying a rationalized post-synthetic grafting methodology. The removal of framework Ge atoms from a Ge-BEC zeolite with low concentrations of Ge in the framework (Si/Ge ~ 150) followed by grafting allows the synthesis of Sn-BEC zeolites with Sn atoms positionally biased into the double-4-ring (D4R) crystallographic positions of the BEC framework. Spectroscopic characterization using solid-state nuclear magnetic resonance (NMR) coupled with theoretical calculations revealed that Sn atoms preferentially form open Sn sites in the D4R of Sn-BEC. This observation was supported by IR spectra of adsorbed deuterated acetonitrile (CD3CN), a known titrant of Sn sites in zeolites. The catalytic implications of selective incorporation of open Sn sites in Sn-BEC were probed using the Meerwein–Ponndorf–Verley–Oppenauer (MPVO) reaction. Although the MPVO turnover rates normalized by the total number of open Sn sites were comparable on Sn-BEC and a conventional Sn-Beta catalyst synthesized in fluoride media (Sn-Beta(F)), Sn-BEC demonstrated higher per gram reaction rates because of its larger fraction of open sites compared to Sn-Beta(F). These results highlight the advantage of placing active sites in targeted locations within a zeolite structure. The methodology presented here to selectively place catalytic active sites via sacrificial heteroatoms, such as Ge, can be generalized for the design of many other tetrahedrally-coordinated metal-containing zeolites.},
doi = {10.1039/D0SC03809A},
journal = {Chemical Science},
number = 37,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {9}
}

Journal Article:
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https://doi.org/10.1039/D0SC03809A

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Works referenced in this record:

Ge-Based Hybrid Composites from Ge-Rich Zeolites as Highly Conductive and Stable Electronic Materials
journal, August 2019

  • Rodríguez-Fernández, Aída; Atienzar, Pedro; Martínez, Cristina
  • Chemistry of Materials, Vol. 31, Issue 18
  • DOI: 10.1021/acs.chemmater.9b02696

Synthesis and Characterization of the All-Silica Pure Polymorph C and an Enriched Polymorph B Intergrowth of Zeolite Beta
journal, December 2006

  • Cantín, Ángel; Corma, Avelino; Díaz-Cabañas, María J.
  • Angewandte Chemie International Edition, Vol. 45, Issue 47
  • DOI: 10.1002/anie.200603027

Distinguishing Active Site Identity in Sn-Beta Zeolites Using 31 P MAS NMR of Adsorbed Trimethylphosphine Oxide
journal, February 2018


Synthesis of the Ti−Silicate Form of BEC Polymorph of β-Zeolite Assisted by Molecular Modeling
journal, November 2008

  • Moliner, Manuel; Serna, Pedro; Cantín, Ángel
  • The Journal of Physical Chemistry C, Vol. 112, Issue 49
  • DOI: 10.1021/jp805400u

Single isomerization selectivity of glucose in methanol over Sn-BEC zeolite of homogenous Sn distribution
journal, July 2017


Acid-Base Pairs in Lewis Acidic Zeolites Promote Direct Aldol Reactions by Soft Enolization
journal, July 2015

  • Lewis, Jennifer D.; Van de Vyver, Stijn; Román-Leshkov, Yuriy
  • Angewandte Chemie International Edition, Vol. 54, Issue 34
  • DOI: 10.1002/anie.201502939

Impact of Controlling the Site Distribution of Al Atoms on Catalytic Properties in Ferrierite-Type Zeolites
journal, September 2010

  • Román-Leshkov, Yuriy; Moliner, Manuel; Davis, Mark E.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 4
  • DOI: 10.1021/jp106247g

Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
journal, January 1985

  • Hay, P. Jeffrey; Wadt, Willard R.
  • The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310
  • DOI: 10.1063/1.448975

Snβ-zeolite catalyzed oxido-reduction cascade chemistry with biomass-derived molecules
journal, January 2016

  • Dijkmans, J.; Schutyser, W.; Dusselier, M.
  • Chemical Communications, Vol. 52, Issue 40
  • DOI: 10.1039/C6CC00199H

Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules
journal, January 1971

  • Ditchfield, R.; Hehre, W. J.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 54, Issue 2
  • DOI: 10.1063/1.1674902

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


Tuning the Aluminum Distribution in Zeolites to Increase their Performance in Acid-Catalyzed Reactions
journal, December 2018


High-silica nanocrystalline Beta zeolites: efficient synthesis and catalytic application
journal, January 2016

  • Martínez-Franco, Raquel; Paris, Cecilia; Martínez-Armero, Marta E.
  • Chemical Science, Vol. 7, Issue 1
  • DOI: 10.1039/C5SC03019F

The ADOR mechanism for the synthesis of new zeolites
journal, January 2015

  • Eliášová, Pavla; Opanasenko, Maksym; Wheatley, Paul S.
  • Chemical Society Reviews, Vol. 44, Issue 20
  • DOI: 10.1039/C5CS00045A

Preferential Location of Ge Atoms in Polymorph C of Beta Zeolite (ITQ-17) and Their Structure-Directing Effect: A Computational, XRD, and NMR Spectroscopic Study
journal, December 2002

  • Sastre, German; Vidal-Moya, Jose A.; Blasco, Teresa
  • Angewandte Chemie International Edition, Vol. 41, Issue 24
  • DOI: 10.1002/anie.200290028

Template-controlled acidity and catalytic activity of ferrierite crystals
journal, April 2009


Pure Polymorph C of Zeolite Beta Synthesized by Using Framework Isomorphous Substitution as a Structure-Directing Mechanism
journal, June 2001


Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations
journal, November 1990

  • Wolinski, Krzysztof; Hinton, James F.; Pulay, Peter
  • Journal of the American Chemical Society, Vol. 112, Issue 23
  • DOI: 10.1021/ja00179a005

Uniform Catalytic Site in Sn-β-Zeolite Determined Using X-ray Absorption Fine Structure
journal, September 2005

  • Bare, Simon R.; Kelly, Shelly D.; Sinkler, Wharton
  • Journal of the American Chemical Society, Vol. 127, Issue 37
  • DOI: 10.1021/ja052543k

Active Sites in Sn-Beta for Glucose Isomerization to Fructose and Epimerization to Mannose
journal, May 2014

  • Bermejo-Deval, Ricardo; Orazov, Marat; Gounder, Rajamani
  • ACS Catalysis, Vol. 4, Issue 7, p. 2288-2297
  • DOI: 10.1021/cs500466j

Two new three-dimensional twelve-ring zeolite frameworks of which zeolite beta is a disordered intergrowth
journal, March 1988

  • Treacy, M. M. J.; Newsam, J. M.
  • Nature, Vol. 332, Issue 6161
  • DOI: 10.1038/332249a0

Spontaneous nucleation and growth of pure silica zeolite-? free of connectivity defects
journal, January 1996

  • Camblor, Miguel A.; Corma, Avelino; Valencia, Susana
  • Chemical Communications, Issue 20
  • DOI: 10.1039/cc9960002365

Selective Introduction of Acid Sites in Different Confined Positions in ZSM-5 and Its Catalytic Implications
journal, July 2018


Opportunities in Catalysis over Metal-Zeotypes Enabled by Descriptions of Active Centers Beyond Their Binding Site
journal, July 2020

  • Harris, James W.; Bates, Jason S.; Bukowski, Brandon C.
  • ACS Catalysis, Vol. 10, Issue 16
  • DOI: 10.1021/acscatal.0c02102

Consideration of the Aluminum Distribution in Zeolites in Theoretical and Experimental Catalysis Research
journal, December 2017

  • Knott, Brandon C.; Nimlos, Claire T.; Robichaud, David J.
  • ACS Catalysis, Vol. 8, Issue 2
  • DOI: 10.1021/acscatal.7b03676

Catalysis on solid acids: Mechanism and catalyst descriptors in oligomerization reactions of light alkenes
journal, December 2016


Chemical Routes for the Transformation of Biomass into Chemicals
journal, June 2007

  • Corma, Avelino; Iborra, Sara; Velty, Alexandra
  • Chemical Reviews, Vol. 107, Issue 6, p. 2411-2502
  • DOI: 10.1021/cr050989d

31 P NMR Chemical Shifts of Phosphorus Probes as Reliable and Practical Acidity Scales for Solid and Liquid Catalysts
journal, September 2017


Acid strength and solvation in catalysis by MFI zeolites and effects of the identity, concentration and location of framework heteroatoms
journal, April 2014


Ammonia Titration Methods To Quantify Brønsted Acid Sites in Zeolites Substituted with Aluminum and Boron Heteroatoms
journal, April 2018

  • Kester, Philip M.; Miller, Jeffrey T.; Gounder, Rajamani
  • Industrial & Engineering Chemistry Research, Vol. 57, Issue 19
  • DOI: 10.1021/acs.iecr.8b00933

Al distribution and catalytic performance of ZSM-5 zeolites synthesized with various alcohols
journal, September 2017


Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg
journal, January 1985

  • Hay, P. Jeffrey; Wadt, Willard R.
  • The Journal of Chemical Physics, Vol. 82, Issue 1
  • DOI: 10.1063/1.448799

Sn-Beta zeolites with borate salts catalyse the epimerization of carbohydrates via an intramolecular carbon shift
journal, January 2012

  • Gunther, William R.; Wang, Yuran; Ji, Yuewei
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms2122

Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18
journal, May 1980

  • McLean, A. D.; Chandler, G. S.
  • The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648
  • DOI: 10.1063/1.438980

Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations
journal, July 2001

  • Corma, Avelino; Nemeth, Laszlo T.; Renz, Michael
  • Nature, Vol. 412, Issue 6845
  • DOI: 10.1038/35086546

Direct Observation of Growth Defects in Zeolite Beta
journal, January 2005

  • Wright, Paul A.; Zhou, Wuzong; Pérez-Pariente, Joaquin
  • Journal of the American Chemical Society, Vol. 127, Issue 2
  • DOI: 10.1021/ja043948s

Controlling the Aluminum Distribution in the Zeolite Ferrierite via the Organic Structure Directing Agent
journal, August 2013

  • Pinar, Ana B.; Gómez-Hortigüela, Luis; McCusker, Lynne B.
  • Chemistry of Materials, Vol. 25, Issue 18
  • DOI: 10.1021/cm4018024

Making Nanosized CHA Zeolites with Controlled Al Distribution for Optimizing Methanol-to-Olefin Performance
journal, September 2018

  • Gallego, Eva M.; Li, Chengeng; Paris, Cecilia
  • Chemistry - A European Journal, Vol. 24, Issue 55
  • DOI: 10.1002/chem.201803637

Mechanism of the Meerwein−Ponndorf−Verley−Oppenauer (MPVO) Redox Equilibrium on Sn− and Zr−Beta Zeolite Catalysts
journal, October 2006

  • Boronat, Mercedes; Corma, Avelino; Renz, Michael
  • The Journal of Physical Chemistry B, Vol. 110, Issue 42
  • DOI: 10.1021/jp063249x

Titration and quantification of open and closed Lewis acid sites in Sn-Beta zeolites that catalyze glucose isomerization
journal, March 2016


“Ab initio” synthesis of zeolites for preestablished catalytic reactions
journal, March 2017

  • Gallego, Eva María; Portilla, M. Teresa; Paris, Cecilia
  • Science, Vol. 355, Issue 6329
  • DOI: 10.1126/science.aal0121

Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water
journal, March 2010

  • Moliner, M.; Roman-Leshkov, Y.; Davis, M. E.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 14, p. 6164-6168
  • DOI: 10.1073/pnas.1002358107

Synthesis of reaction‐adapted zeolites as methanol-to-olefins catalysts with mimics of reaction intermediates as organic structure‐directing agents
journal, July 2018

  • Li, Chengeng; Paris, Cecilia; Martínez-Triguero, Joaquín
  • Nature Catalysis, Vol. 1, Issue 7
  • DOI: 10.1038/s41929-018-0104-7

Increasing the stability of the Ge-containing extra-large pore ITQ-33 zeolite by post-synthetic acid treatments
journal, September 2018

  • Rodríguez-Fernández, Aída; Llopis, Francisco J.; Martínez, Cristina
  • Microporous and Mesoporous Materials, Vol. 267
  • DOI: 10.1016/j.micromeso.2018.03.006

Control of the Al Distribution in the Framework of ZSM-5 Zeolite and Its Evaluation by Solid-State NMR Technique and Catalytic Properties
journal, June 2015

  • Yokoi, Toshiyuki; Mochizuki, Hiroshi; Namba, Seitaro
  • The Journal of Physical Chemistry C, Vol. 119, Issue 27
  • DOI: 10.1021/acs.jpcc.5b03289

Structural Characterization of Zeolite Beta
journal, December 1988

  • Newsam, J. M.; Treacy, M. M. J.; Koetsier, W. T.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 420, Issue 1859
  • DOI: 10.1098/rspa.1988.0131

Conversion of Methanol to Olefins over H-ZSM-5 Zeolite: Reaction Pathway Is Related to the Framework Aluminum Siting
journal, September 2016


Activation of Carbonyl-Containing Molecules with Solid Lewis Acids in Aqueous Media
journal, October 2011

  • Román-Leshkov, Yuriy; Davis, Mark E.
  • ACS Catalysis, Vol. 1, Issue 11
  • DOI: 10.1021/cs200411d

Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water
journal, October 2010

  • Román-Leshkov, Yuriy; Moliner, Manuel; Labinger, Jay A.
  • Angewandte Chemie International Edition, Vol. 49, Issue 47, p. 8954-8957
  • DOI: 10.1002/anie.201004689

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527